JP5675899B2 - Conductive member - Google Patents
Conductive member Download PDFInfo
- Publication number
- JP5675899B2 JP5675899B2 JP2013132185A JP2013132185A JP5675899B2 JP 5675899 B2 JP5675899 B2 JP 5675899B2 JP 2013132185 A JP2013132185 A JP 2013132185A JP 2013132185 A JP2013132185 A JP 2013132185A JP 5675899 B2 JP5675899 B2 JP 5675899B2
- Authority
- JP
- Japan
- Prior art keywords
- copper
- aqueous solution
- copper fine
- fine particle
- conductive member
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000010949 copper Substances 0.000 claims description 240
- 229910052802 copper Inorganic materials 0.000 claims description 206
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 203
- 239000010419 fine particle Substances 0.000 claims description 163
- 239000007864 aqueous solution Substances 0.000 claims description 144
- 239000002270 dispersing agent Substances 0.000 claims description 59
- 238000006722 reduction reaction Methods 0.000 claims description 43
- 239000006185 dispersion Substances 0.000 claims description 34
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 22
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical group OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 22
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 21
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 20
- 229910001431 copper ion Inorganic materials 0.000 claims description 20
- 239000000758 substrate Substances 0.000 claims description 19
- 238000010304 firing Methods 0.000 claims description 16
- 239000002245 particle Substances 0.000 claims description 14
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 13
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 claims description 12
- 239000011164 primary particle Substances 0.000 claims description 12
- -1 propionammonium Chemical compound 0.000 claims description 12
- PYMYPHUHKUWMLA-UHFFFAOYSA-N arabinose Natural products OCC(O)C(O)C(O)C=O PYMYPHUHKUWMLA-UHFFFAOYSA-N 0.000 claims description 11
- SRBFZHDQGSBBOR-UHFFFAOYSA-N beta-D-Pyranose-Lyxose Natural products OC1COC(O)C(O)C1O SRBFZHDQGSBBOR-UHFFFAOYSA-N 0.000 claims description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 11
- 238000001914 filtration Methods 0.000 claims description 11
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 11
- 238000000926 separation method Methods 0.000 claims description 11
- SRBFZHDQGSBBOR-IOVATXLUSA-N D-xylopyranose Chemical compound O[C@@H]1COC(O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-IOVATXLUSA-N 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- 239000012528 membrane Substances 0.000 claims description 10
- 239000003002 pH adjusting agent Substances 0.000 claims description 10
- 150000005846 sugar alcohols Polymers 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 9
- 229910021529 ammonia Inorganic materials 0.000 claims description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 9
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 9
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 9
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 9
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 9
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 8
- 239000001099 ammonium carbonate Substances 0.000 claims description 8
- 235000011187 glycerol Nutrition 0.000 claims description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 8
- 239000005750 Copper hydroxide Substances 0.000 claims description 7
- 229910001956 copper hydroxide Inorganic materials 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 7
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 claims description 6
- PYMYPHUHKUWMLA-WDCZJNDASA-N arabinose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)C=O PYMYPHUHKUWMLA-WDCZJNDASA-N 0.000 claims description 6
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 6
- YEOCHZFPBYUXMC-UHFFFAOYSA-L copper benzoate Chemical compound [Cu+2].[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1 YEOCHZFPBYUXMC-UHFFFAOYSA-L 0.000 claims description 6
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 6
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 6
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 6
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 5
- 239000005695 Ammonium acetate Substances 0.000 claims description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 229920002873 Polyethylenimine Polymers 0.000 claims description 5
- 150000001298 alcohols Chemical class 0.000 claims description 5
- 229940043376 ammonium acetate Drugs 0.000 claims description 5
- 235000019257 ammonium acetate Nutrition 0.000 claims description 5
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 5
- 230000018044 dehydration Effects 0.000 claims description 5
- 238000006297 dehydration reaction Methods 0.000 claims description 5
- 238000004108 freeze drying Methods 0.000 claims description 5
- 238000001223 reverse osmosis Methods 0.000 claims description 5
- 238000000108 ultra-filtration Methods 0.000 claims description 5
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 4
- ARXKVVRQIIOZGF-UHFFFAOYSA-N 1,2,4-butanetriol Chemical compound OCCC(O)CO ARXKVVRQIIOZGF-UHFFFAOYSA-N 0.000 claims description 4
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 4
- 108010010803 Gelatin Proteins 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- 229920002472 Starch Polymers 0.000 claims description 4
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 4
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 4
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 4
- 229920000159 gelatin Polymers 0.000 claims description 4
- 239000008273 gelatin Substances 0.000 claims description 4
- 235000019322 gelatine Nutrition 0.000 claims description 4
- 235000011852 gelatine desserts Nutrition 0.000 claims description 4
- 229920002401 polyacrylamide Polymers 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 239000008107 starch Substances 0.000 claims description 4
- 235000019698 starch Nutrition 0.000 claims description 4
- HDTRYLNUVZCQOY-UHFFFAOYSA-N α-D-glucopyranosyl-α-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OC1C(O)C(O)C(O)C(CO)O1 HDTRYLNUVZCQOY-UHFFFAOYSA-N 0.000 claims description 3
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 claims description 3
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims description 3
- OTJFQRMIRKXXRS-UHFFFAOYSA-N (hydroxymethylamino)methanol Chemical group OCNCO OTJFQRMIRKXXRS-UHFFFAOYSA-N 0.000 claims description 3
- ORTVZLZNOYNASJ-UPHRSURJSA-N (z)-but-2-ene-1,4-diol Chemical compound OC\C=C/CO ORTVZLZNOYNASJ-UPHRSURJSA-N 0.000 claims description 3
- ZWVMLYRJXORSEP-UHFFFAOYSA-N 1,2,6-Hexanetriol Chemical compound OCCCCC(O)CO ZWVMLYRJXORSEP-UHFFFAOYSA-N 0.000 claims description 3
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 3
- DBTMGCOVALSLOR-UHFFFAOYSA-N 32-alpha-galactosyl-3-alpha-galactosyl-galactose Natural products OC1C(O)C(O)C(CO)OC1OC1C(O)C(OC2C(C(CO)OC(O)C2O)O)OC(CO)C1O DBTMGCOVALSLOR-UHFFFAOYSA-N 0.000 claims description 3
- GUBGYTABKSRVRQ-XLOQQCSPSA-N Alpha-Lactose Chemical compound O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)O[C@H](O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-XLOQQCSPSA-N 0.000 claims description 3
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 3
- OCUCCJIRFHNWBP-IYEMJOQQSA-L Copper gluconate Chemical compound [Cu+2].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O OCUCCJIRFHNWBP-IYEMJOQQSA-L 0.000 claims description 3
- YTBSYETUWUMLBZ-UHFFFAOYSA-N D-Erythrose Natural products OCC(O)C(O)C=O YTBSYETUWUMLBZ-UHFFFAOYSA-N 0.000 claims description 3
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 3
- YPZMPEPLWKRVLD-PJEQPVAWSA-N D-Glycero-D-gulo-Heptose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)[C@@H](O)C=O YPZMPEPLWKRVLD-PJEQPVAWSA-N 0.000 claims description 3
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 claims description 3
- WQZGKKKJIJFFOK-WHZQZERISA-N D-aldose Chemical compound OC[C@H]1OC(O)[C@@H](O)[C@@H](O)[C@H]1O WQZGKKKJIJFFOK-WHZQZERISA-N 0.000 claims description 3
- WQZGKKKJIJFFOK-IVMDWMLBSA-N D-allopyranose Chemical compound OC[C@H]1OC(O)[C@H](O)[C@H](O)[C@@H]1O WQZGKKKJIJFFOK-IVMDWMLBSA-N 0.000 claims description 3
- HEBKCHPVOIAQTA-QWWZWVQMSA-N D-arabinitol Chemical compound OC[C@@H](O)C(O)[C@H](O)CO HEBKCHPVOIAQTA-QWWZWVQMSA-N 0.000 claims description 3
- YTBSYETUWUMLBZ-IUYQGCFVSA-N D-erythrose Chemical compound OC[C@@H](O)[C@@H](O)C=O YTBSYETUWUMLBZ-IUYQGCFVSA-N 0.000 claims description 3
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims description 3
- RXVWSYJTUUKTEA-UHFFFAOYSA-N D-maltotriose Natural products OC1C(O)C(OC(C(O)CO)C(O)C(O)C=O)OC(CO)C1OC1C(O)C(O)C(O)C(CO)O1 RXVWSYJTUUKTEA-UHFFFAOYSA-N 0.000 claims description 3
- WQZGKKKJIJFFOK-QTVWNMPRSA-N D-mannopyranose Chemical compound OC[C@H]1OC(O)[C@@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-QTVWNMPRSA-N 0.000 claims description 3
- HMFHBZSHGGEWLO-SOOFDHNKSA-N D-ribofuranose Chemical compound OC[C@H]1OC(O)[C@H](O)[C@@H]1O HMFHBZSHGGEWLO-SOOFDHNKSA-N 0.000 claims description 3
- ZAQJHHRNXZUBTE-NQXXGFSBSA-N D-ribulose Chemical compound OC[C@@H](O)[C@@H](O)C(=O)CO ZAQJHHRNXZUBTE-NQXXGFSBSA-N 0.000 claims description 3
- ZAQJHHRNXZUBTE-UHFFFAOYSA-N D-threo-2-Pentulose Natural products OCC(O)C(O)C(=O)CO ZAQJHHRNXZUBTE-UHFFFAOYSA-N 0.000 claims description 3
- YTBSYETUWUMLBZ-QWWZWVQMSA-N D-threose Chemical compound OC[C@@H](O)[C@H](O)C=O YTBSYETUWUMLBZ-QWWZWVQMSA-N 0.000 claims description 3
- ZAQJHHRNXZUBTE-WUJLRWPWSA-N D-xylulose Chemical compound OC[C@@H](O)[C@H](O)C(=O)CO ZAQJHHRNXZUBTE-WUJLRWPWSA-N 0.000 claims description 3
- 239000004386 Erythritol Substances 0.000 claims description 3
- UNXHWFMMPAWVPI-UHFFFAOYSA-N Erythritol Natural products OCC(O)C(O)CO UNXHWFMMPAWVPI-UHFFFAOYSA-N 0.000 claims description 3
- 206010056474 Erythrosis Diseases 0.000 claims description 3
- 229930091371 Fructose Natural products 0.000 claims description 3
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 claims description 3
- 239000005715 Fructose Substances 0.000 claims description 3
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 3
- AYRXSINWFIIFAE-SCLMCMATSA-N Isomaltose Natural products OC[C@H]1O[C@H](OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O)[C@@H](O)[C@@H](O)[C@@H]1O AYRXSINWFIIFAE-SCLMCMATSA-N 0.000 claims description 3
- LKDRXBCSQODPBY-AMVSKUEXSA-N L-(-)-Sorbose Chemical compound OCC1(O)OC[C@H](O)[C@@H](O)[C@@H]1O LKDRXBCSQODPBY-AMVSKUEXSA-N 0.000 claims description 3
- WQZGKKKJIJFFOK-VSOAQEOCSA-N L-altropyranose Chemical compound OC[C@@H]1OC(O)[C@H](O)[C@@H](O)[C@H]1O WQZGKKKJIJFFOK-VSOAQEOCSA-N 0.000 claims description 3
- GUBGYTABKSRVRQ-QKKXKWKRSA-N Lactose Natural products OC[C@H]1O[C@@H](O[C@H]2[C@H](O)[C@@H](O)C(O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@H]1O GUBGYTABKSRVRQ-QKKXKWKRSA-N 0.000 claims description 3
- 229930195725 Mannitol Natural products 0.000 claims description 3
- AKNUHUCEWALCOI-UHFFFAOYSA-N N-ethyldiethanolamine Chemical compound OCCN(CC)CCO AKNUHUCEWALCOI-UHFFFAOYSA-N 0.000 claims description 3
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 claims description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- JVWLUVNSQYXYBE-UHFFFAOYSA-N Ribitol Natural products OCC(C)C(O)C(O)CO JVWLUVNSQYXYBE-UHFFFAOYSA-N 0.000 claims description 3
- PYMYPHUHKUWMLA-LMVFSUKVSA-N Ribose Natural products OC[C@@H](O)[C@@H](O)[C@@H](O)C=O PYMYPHUHKUWMLA-LMVFSUKVSA-N 0.000 claims description 3
- 229920002125 Sokalan® Polymers 0.000 claims description 3
- HDTRYLNUVZCQOY-WSWWMNSNSA-N Trehalose Natural products O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 HDTRYLNUVZCQOY-WSWWMNSNSA-N 0.000 claims description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 3
- SLINHMUFWFWBMU-UHFFFAOYSA-N Triisopropanolamine Chemical compound CC(O)CN(CC(C)O)CC(C)O SLINHMUFWFWBMU-UHFFFAOYSA-N 0.000 claims description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 3
- TVXBFESIOXBWNM-UHFFFAOYSA-N Xylitol Natural products OCCC(O)C(O)C(O)CCO TVXBFESIOXBWNM-UHFFFAOYSA-N 0.000 claims description 3
- ITBPIKUGMIZTJR-UHFFFAOYSA-N [bis(hydroxymethyl)amino]methanol Chemical compound OCN(CO)CO ITBPIKUGMIZTJR-UHFFFAOYSA-N 0.000 claims description 3
- HDTRYLNUVZCQOY-LIZSDCNHSA-N alpha,alpha-trehalose Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 HDTRYLNUVZCQOY-LIZSDCNHSA-N 0.000 claims description 3
- HMFHBZSHGGEWLO-UHFFFAOYSA-N alpha-D-Furanose-Ribose Natural products OCC1OC(O)C(O)C1O HMFHBZSHGGEWLO-UHFFFAOYSA-N 0.000 claims description 3
- WQZGKKKJIJFFOK-PHYPRBDBSA-N alpha-D-galactose Chemical compound OC[C@H]1O[C@H](O)[C@H](O)[C@@H](O)[C@H]1O WQZGKKKJIJFFOK-PHYPRBDBSA-N 0.000 claims description 3
- SRBFZHDQGSBBOR-STGXQOJASA-N alpha-D-lyxopyranose Chemical compound O[C@@H]1CO[C@H](O)[C@@H](O)[C@H]1O SRBFZHDQGSBBOR-STGXQOJASA-N 0.000 claims description 3
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 3
- BVCZEBOGSOYJJT-UHFFFAOYSA-N ammonium carbamate Chemical compound [NH4+].NC([O-])=O BVCZEBOGSOYJJT-UHFFFAOYSA-N 0.000 claims description 3
- VZTDIZULWFCMLS-UHFFFAOYSA-N ammonium formate Chemical compound [NH4+].[O-]C=O VZTDIZULWFCMLS-UHFFFAOYSA-N 0.000 claims description 3
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 claims description 3
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 3
- BMRWNKZVCUKKSR-UHFFFAOYSA-N butane-1,2-diol Chemical compound CCC(O)CO BMRWNKZVCUKKSR-UHFFFAOYSA-N 0.000 claims description 3
- OWBTYPJTUOEWEK-UHFFFAOYSA-N butane-2,3-diol Chemical compound CC(O)C(C)O OWBTYPJTUOEWEK-UHFFFAOYSA-N 0.000 claims description 3
- KXDHJXZQYSOELW-UHFFFAOYSA-N carbonic acid monoamide Natural products NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 3
- 229940108925 copper gluconate Drugs 0.000 claims description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 3
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 3
- SVOAENZIOKPANY-CVBJKYQLSA-L copper;(z)-octadec-9-enoate Chemical compound [Cu+2].CCCCCCCC\C=C/CCCCCCCC([O-])=O.CCCCCCCC\C=C/CCCCCCCC([O-])=O SVOAENZIOKPANY-CVBJKYQLSA-L 0.000 claims description 3
- RSJOBNMOMQFPKQ-UHFFFAOYSA-L copper;2,3-dihydroxybutanedioate Chemical compound [Cu+2].[O-]C(=O)C(O)C(O)C([O-])=O RSJOBNMOMQFPKQ-UHFFFAOYSA-L 0.000 claims description 3
- HFDWIMBEIXDNQS-UHFFFAOYSA-L copper;diformate Chemical compound [Cu+2].[O-]C=O.[O-]C=O HFDWIMBEIXDNQS-UHFFFAOYSA-L 0.000 claims description 3
- QYCVHILLJSYYBD-UHFFFAOYSA-L copper;oxalate Chemical compound [Cu+2].[O-]C(=O)C([O-])=O QYCVHILLJSYYBD-UHFFFAOYSA-L 0.000 claims description 3
- QNZRVYCYEMYQMD-UHFFFAOYSA-N copper;pentane-2,4-dione Chemical compound [Cu].CC(=O)CC(C)=O QNZRVYCYEMYQMD-UHFFFAOYSA-N 0.000 claims description 3
- HEBKCHPVOIAQTA-NGQZWQHPSA-N d-xylitol Chemical compound OC[C@H](O)C(O)[C@H](O)CO HEBKCHPVOIAQTA-NGQZWQHPSA-N 0.000 claims description 3
- FWBOFUGDKHMVPI-UHFFFAOYSA-K dicopper;2-oxidopropane-1,2,3-tricarboxylate Chemical compound [Cu+2].[Cu+2].[O-]C(=O)CC([O-])(C([O-])=O)CC([O-])=O FWBOFUGDKHMVPI-UHFFFAOYSA-K 0.000 claims description 3
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 3
- LVTYICIALWPMFW-UHFFFAOYSA-N diisopropanolamine Chemical compound CC(O)CNCC(C)O LVTYICIALWPMFW-UHFFFAOYSA-N 0.000 claims description 3
- 229940043276 diisopropanolamine Drugs 0.000 claims description 3
- UNXHWFMMPAWVPI-ZXZARUISSA-N erythritol Chemical compound OC[C@H](O)[C@H](O)CO UNXHWFMMPAWVPI-ZXZARUISSA-N 0.000 claims description 3
- 235000019414 erythritol Nutrition 0.000 claims description 3
- 229940009714 erythritol Drugs 0.000 claims description 3
- UQPHVQVXLPRNCX-UHFFFAOYSA-N erythrulose Chemical compound OCC(O)C(=O)CO UQPHVQVXLPRNCX-UHFFFAOYSA-N 0.000 claims description 3
- 238000005188 flotation Methods 0.000 claims description 3
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- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 3
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
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- 239000003513 alkali Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- XJMWHXZUIGHOBA-UHFFFAOYSA-N azane;propanoic acid Chemical compound N.CCC(O)=O XJMWHXZUIGHOBA-UHFFFAOYSA-N 0.000 description 2
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- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 2
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 2
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- 230000002411 adverse Effects 0.000 description 1
- 230000004931 aggregating effect Effects 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- RAVDFEPNANSXII-UHFFFAOYSA-N butane-1,2,4-triol;propane-1,2,3-triol Chemical compound OCC(O)CO.OCCC(O)CO RAVDFEPNANSXII-UHFFFAOYSA-N 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
- AEJIMXVJZFYIHN-UHFFFAOYSA-N copper;dihydrate Chemical compound O.O.[Cu] AEJIMXVJZFYIHN-UHFFFAOYSA-N 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
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- 125000000524 functional group Chemical group 0.000 description 1
- CBCIHIVRDWLAME-UHFFFAOYSA-N hexanitrodiphenylamine Chemical compound [O-][N+](=O)C1=CC([N+](=O)[O-])=CC([N+]([O-])=O)=C1NC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O CBCIHIVRDWLAME-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
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- 239000012299 nitrogen atmosphere Substances 0.000 description 1
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
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Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Electrolytic Production Of Metals (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
- Colloid Chemistry (AREA)
- Powder Metallurgy (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Manufacturing Of Printed Wiring (AREA)
- Conductive Materials (AREA)
- Manufacturing Of Electric Cables (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Description
本発明は、ナノサイズの銅微粒子が水溶液中に分散されている銅微粒子分散水溶液を基材上に配置して、乾燥後に焼成して形成された導電部材に関する。 The present invention relates to a conductive member formed by disposing a copper fine particle-dispersed aqueous solution in which nano-sized copper fine particles are dispersed in an aqueous solution on a substrate and firing after drying.
ナノサイズ(粒径が1μm以下)の金属、合金等の微粒子は、バルク材料にはない様々な特異な特性を持つことが知られている。そしてこの特性を生かした様々な工学的応用が、現在、エレクトロニクス、バイオ、エネルギー等の各分野で、大いに期待されている。 It is known that nano-sized (particle size is 1 μm or less) fine particles such as metals and alloys have various unique characteristics not found in bulk materials. Various engineering applications that take advantage of this property are now highly expected in fields such as electronics, biotechnology, and energy.
中でも、銅及びその合金からなるナノサイズの微粒子は、導電回路、バンプ、ビア、パッド等の実装部品の形成材料、高密度磁気記憶媒体やアンテナ用の磁性素子、ガス改質フィルタや燃料電池電極用の触媒材料として、大いに期待されている。 Among these, nano-sized fine particles made of copper and its alloys are used as materials for forming mounting parts such as conductive circuits, bumps, vias, pads, magnetic elements for high-density magnetic storage media and antennas, gas reforming filters, and fuel cell electrodes. It is highly expected as a catalyst material.
また、最近では、銅微粒子を含有するインクを使用して、配線パターンをインクジェットプリンタ法により形成し、焼成して配線を形成する技術が注目されている。しかし、インクジェットプリンタ法に使用するインクとして、銅微粒子を含有するインクを使用する場合、インク中において分散性が長期間保たれることが重要である。そのため、インク中において銅微粒子分散性を長期間保つ銅微粒子分散溶液、及び該銅微粒子分散溶液の製造方法が提案されている。 In recent years, attention has been focused on a technique for forming a wiring pattern by an ink jet printer method using an ink containing copper fine particles and baking it to form a wiring. However, when an ink containing copper fine particles is used as the ink used in the ink jet printer method, it is important that the dispersibility is maintained in the ink for a long period of time. Therefore, a copper fine particle dispersion solution that maintains the copper fine particle dispersibility in the ink for a long time and a method for producing the copper fine particle dispersion solution have been proposed.
特許文献1では、銅の酸化物、水酸化物または塩をポリエチレングリコールまたは1,2−エタンジオール(エチレングリコール)溶液中で、核生成のためのパラジウムイオンと、分散剤としてのポリエチレンイミンを添加して、加熱還元することにより、液相中で銅微粒子を合成する方法が提案されている。
また、特許文献2では、アルキルアミンを分散剤に使用して、アミン化合物で覆われた金属微粒子を製造する方法及び該金属微粒子分散溶液が提案されている。また、特許文献3には、セルロース誘導体を含む水溶液中で金属イオンを還元することにより、セルロース誘導体で覆われた金属微粒子を製造する方法及び該微粒子分散溶液が提案されている。
In Patent Document 1, copper oxide, hydroxide or salt is added in polyethylene glycol or 1,2-ethanediol (ethylene glycol) solution, and palladium ions for nucleation and polyethyleneimine as a dispersant are added. Thus, a method for synthesizing copper fine particles in a liquid phase by heat reduction has been proposed.
Patent Document 2 proposes a method for producing metal fine particles covered with an amine compound by using alkylamine as a dispersant and the metal fine particle dispersion solution. Patent Document 3 proposes a method for producing metal fine particles covered with a cellulose derivative by reducing metal ions in an aqueous solution containing the cellulose derivative, and the fine particle dispersion.
一方、上述のインクジェット回路形成技術のように金属微粒子の焼成により導電性の金属部材を形成する場合や、微粒子焼成体をガス改質フィルタに使用する場合などには、焼成後の粒子焼成体において、微粒子自体が表面に露出して粒子同士が直接接合している必要がある。そのため、これらの技術に使用される微粒子については、その表面に存在する分散剤等が、熱処理時に容易に分解除去される必要がある。
尚、下記特許文献4には、酸化銅を原料として、分散剤、pH調製溶液、及び還元剤を添加してpHを10以上とした後に、加熱還流して銅微粒子を析出する方法が開示されている。
下記特許文献5には、銅イオン含有水溶液とアルカリ溶液とを反応させて水酸化銅スラリーとし、該水酸化銅スラリーに還元剤を添加して第一還元処理で亜酸化銅スラリーとし、該亜酸化銅スラリーを回収、洗浄して得た亜酸化銅スラリーに還元剤を添加して第二還元処理で銅粉を得る銅粉製造方法が開示されている。
On the other hand, in the case where a conductive metal member is formed by firing fine metal particles as in the ink jet circuit forming technique described above, or when the fine particle fired body is used for a gas reforming filter, It is necessary that the fine particles themselves are exposed on the surface and the particles are directly bonded to each other. Therefore, for the fine particles used in these techniques, the dispersant and the like present on the surface thereof must be easily decomposed and removed during the heat treatment.
Patent Document 4 listed below discloses a method in which copper oxide is used as a raw material, a dispersant, a pH adjusting solution, and a reducing agent are added to adjust the pH to 10 or more, and then heated to reflux to precipitate copper fine particles. ing.
In Patent Document 5 below, a copper ion-containing aqueous solution and an alkali solution are reacted to form a copper hydroxide slurry, and a reducing agent is added to the copper hydroxide slurry to form a cuprous oxide slurry by a first reduction treatment. The copper powder manufacturing method which adds a reducing agent to the cuprous oxide slurry obtained by collect | recovering and wash | cleaning a copper oxide slurry, and obtains copper powder by a 2nd reduction process is disclosed.
上記したように、金属微粒子分散インクのパターニングと焼成とにより、導電性配線パターンやフィルタ等を形成する場合、分散性を考慮した溶媒を選択する必要があり、また分散性向上のために使用した分散剤が熱処理時に容易に分解除去される必要がある。
しかしながら、上述の分散剤で覆われた金属微粒子では250℃以上の高温で熱処理をしなければ、分散剤を分解除去して導電性の良好な導電性配線等を得ることができないという問題点があった。
また、上記したような高温での熱処理を行うと、金属微粒子をパターニングした基板(例えば、汎用樹脂基板)に設置されている他の部品が壊れたり、更に基板自体が溶融もしくは変形したりしてしまうという問題点もあった。
As described above, when forming a conductive wiring pattern, filter, etc. by patterning and baking of metal fine particle dispersed ink, it is necessary to select a solvent in consideration of dispersibility, and it was used for improving dispersibility. The dispersant must be easily decomposed and removed during the heat treatment.
However, the metal fine particles covered with the above-described dispersant have a problem that unless the heat treatment is performed at a high temperature of 250 ° C. or higher, the dispersant cannot be decomposed and removed to obtain a conductive wiring having good conductivity. there were.
In addition, when heat treatment is performed at a high temperature as described above, other components installed on a substrate (for example, a general-purpose resin substrate) patterned with metal fine particles may be broken, or the substrate itself may be melted or deformed. There was also a problem of end.
一方、金属微粒子が分散剤で覆われていない、金属微粒子分散溶液を使用した場合、分散溶液中で互いに凝集した金属微粒子がインクジェットプリンタのノズルを閉塞させるという問題があった。また、焼結時に金属微粒子同士が不均一に凝集して焼結性が不均一になるという問題があった。
また、焼結時にパターニングされた銅微粒子分散水溶液中に、銅イオンを形成する化合物、分散剤、及びpH調整剤に、銅元素、炭素原子、水素原子、酸素原子、及び窒素原子以外の原子を含む化合物が含まれていると容易に分解除去されず、得られる焼結体の導電性が低下し、またはワレ等が発生し易いという問題点があった。
On the other hand, when the metal fine particle dispersion solution in which the metal fine particles are not covered with the dispersant is used, there is a problem that the metal fine particles aggregated with each other in the dispersion solution block the nozzles of the ink jet printer. Further, there has been a problem that the metal fine particles are aggregated non-uniformly during sintering and the sinterability becomes non-uniform.
Moreover, in the copper fine particle dispersion aqueous solution patterned at the time of sintering, compounds other than copper element, carbon atom, hydrogen atom, oxygen atom, and nitrogen atom are added to the compound, dispersant, and pH adjuster that form copper ions. If the contained compound is contained, it is not easily decomposed and removed, and there is a problem that the conductivity of the obtained sintered body is lowered or cracking or the like is likely to occur.
本発明は、上記問題点を解決し、還元反応終了後の還元反応水溶液をそのまま、又は更に一部の水分等の除去による濃縮操作により得られる、分散性の高い銅微粒子分散水溶液を基材上にパターニング、配置等して乾燥後、250℃以下の比較的低温で焼成しても導電性に優れ、不純物の少ない導電部材、更に、焼成の際に水素ガス等の還元性雰囲気下を必ずしも必要とせず、不活性ガス雰囲気下で焼成が可能である銅微粒子分散水溶液を基材上に配置して、乾燥後に焼成して形成された導電部材を提供することを目的とする。 The present invention solves the above-mentioned problems, and provides a highly dispersible aqueous solution of copper fine particles on a substrate, which is obtained by performing a reduction reaction aqueous solution after completion of the reduction reaction as it is or by a concentration operation by removing a part of moisture and the like. After drying by patterning, arranging, etc., it is necessary to have a conductive member that is excellent in conductivity and has few impurities even when fired at a relatively low temperature of 250 ° C. or lower, and further requires a reducing atmosphere such as hydrogen gas during firing. Instead, an object of the present invention is to provide a conductive member formed by disposing a copper fine particle-dispersed aqueous solution that can be fired in an inert gas atmosphere on a substrate and firing it after drying.
本発明者らは上述した従来の問題点について鋭意研究を重ねた結果、分散剤及びpH調整剤を添加した、銅アミン錯体を含み、かつ銅、炭素原子、水素原子、酸素原子、及び窒素原子以外の原子を含む化合物を含まない水溶液中で、銅イオンを電解還元して得られる分散性が良好な銅微粒子分散水溶液を、250℃以下の比較的低温で焼成しても、得られる導電部材は導電性に優れ、不純物が少ないことを見出し、本発明に到達した。 As a result of intensive studies on the above-described conventional problems, the present inventors have added a dispersant and a pH adjuster, contain a copper amine complex, and contain copper, carbon atoms, hydrogen atoms, oxygen atoms, and nitrogen atoms. Conductive member obtained by firing a copper fine particle dispersed aqueous solution with good dispersibility obtained by electrolytic reduction of copper ions in an aqueous solution containing no compound containing any other atoms at a relatively low temperature of 250 ° C. or lower Was found to be excellent in conductivity and low in impurities, and reached the present invention.
すなわち本発明は、以下の(1)ないし(12)に記載する発明を要旨とする。
(1)一次粒子の平均粒径1〜150nmの銅微粒子が少なくともその表面の一部が分散剤で覆われて水溶液中に分散されている、銅微粒子分散水溶液であって、
(i)銅イオンを、分散剤の存在下でpH調整剤によりpH9.2以上に調整したアンモニア水溶液中でアンモニアと下記反応をさせ、水溶性の銅アンミン錯体を得る工程(工程1)、
Cu2++4NH3 → [Cu(NH3)4]2+
又は Cu2++4NH4(OH) → [Cu(NH3)4]2+ +4H2O
(ii)前記工程1で得られた銅アンミン錯体を含む還元反応水溶液において、下記の銅アンミン錯体の電解還元反応により、少なくとも表面の一部が分散剤で覆われた銅微粒子を形成する工程(工程2)、
Cu(NH3)4 2++2e− → Cu+2NH3
又は Cu(NH3)4 2++2e−+2H2O→ Cu+2NH4(OH)
を含み、前記還元反応の系において、銅元素、炭素原子、水素原子、酸素原子、及び窒素原子以外の原子を含む化合物を含まずに製造された銅微粒子分散水溶液を
基材上に配置して、乾燥後に焼成して形成されたことを特徴とする導電部材。
That is, the gist of the present invention is the invention described in the following (1) to (12).
(1) A copper fine particle-dispersed aqueous solution in which copper fine particles having an average particle diameter of 1 to 150 nm of primary particles are dispersed in an aqueous solution in which at least part of the surface is covered with a dispersant,
(I) a step of obtaining a water-soluble copper ammine complex by reacting copper ions with ammonia in an aqueous ammonia solution adjusted to a pH of 9.2 or more with a pH adjuster in the presence of a dispersant (step 1);
Cu 2+ + 4NH 3 → [Cu (NH 3 ) 4 ] 2+
Or Cu 2+ + 4NH 4 (OH) → [Cu (NH 3 ) 4 ] 2+ + 4H 2 O
(Ii) In the reduction reaction aqueous solution containing the copper ammine complex obtained in the step 1, the step of forming copper fine particles in which at least a part of the surface is covered with the dispersant by the electrolytic reduction reaction of the following copper ammine complex ( Step 2),
Cu (NH 3 ) 4 2+ + 2e − → Cu + 2NH 3
Or Cu (NH 3 ) 4 2+ + 2e − + 2H 2 O → Cu + 2NH 4 (OH)
In the reduction reaction system, a copper fine particle dispersed aqueous solution produced without containing a compound containing an element other than a copper element, a carbon atom, a hydrogen atom, an oxygen atom, and a nitrogen atom is disposed on a substrate. A conductive member formed by firing after drying.
(2)前記乾燥後に温度250℃以下で焼成して形成され、電気抵抗が6.0×10−5Ω・cm未満であることを特徴とする、前記(1)に記載の導電部材。
(3)前記基材上に配置される銅微粒子分散水溶液中の銅微粒子が、前記工程2において、還元反応水溶液中に設けられたアノードとカソード間に電位を加えることによりカソード表面付近に析出された銅微粒子であることを特徴とする、前記(1)又は(2)に記載の導電部材。
(4)前記pH調整剤が酢酸アンモニウム、炭酸アンモニウム、蟻酸アンモニウム、プロピオンアンモニウム、炭酸水素アンモニウム、シュウ酸アンモニウム、カルバミン酸アンモニウムから選択された1種又は2種以上である、前記(1)ないし(3)のいずれかに記載の導電部材。
(5)前記銅イオンが、水酸化銅、硝酸銅、亜硝酸塩、酢酸銅、蟻酸銅、クエン酸銅、シュウ酸銅、グルコン酸銅、安息香酸銅、酒石酸銅、オレイン酸銅、アセチルアセトン銅から選択された1種又は2種以上から得られたものである、前記(1)ないし(4)のいずれかに記載の導電部材。
(6)前記分散剤が、ポリビニルピロリドン、ポリエチレンイミン、ポリアクリル酸、カルボキシメチルセルロース、ポリアクリルアミド、ポリビニルアルコール、ポリエチレングリコール、ポリエチレンオキシド、デンプン、及びゼラチンの中から選択される1種又は2種以上の有機化合物であることを特徴とする、前記(1)ないし(5)のいずれかに記載の導電部材。
(7)前記分散剤の添加量が、銅イオン100重量部に対して0.1〜500重量部であることを特徴とする、前記(1)ないし(6)のいずれかに記載の導電部材。
(8)前記基材上に配置される銅微粒子分散水溶液が、還元反応後の銅微粒子分散水溶液から、銅微粒子を遠心分離、濾過、圧搾分離、浮上分離、又は沈降分離より回収した後、該回収した銅微粒子をpHが9〜14の範囲のアルカリ水溶液中に分散させて得られた銅微粒子分散水溶液であることを特徴とする、前記(1)ないし(7)のいずれかに記載の導電部材。
(2) The conductive member according to (1), which is formed by firing at a temperature of 250 ° C. or less after the drying, and has an electric resistance of less than 6.0 × 10 −5 Ω · cm.
(3) The copper fine particles in the copper fine particle dispersed aqueous solution arranged on the substrate are deposited near the cathode surface by applying a potential between the anode and the cathode provided in the reduction reaction aqueous solution in the step 2. The conductive member according to (1) or (2), wherein the conductive member is a copper fine particle.
(4) The pH adjuster is one or more selected from ammonium acetate, ammonium carbonate, ammonium formate, ammonium propionate, ammonium hydrogen carbonate, ammonium oxalate, and ammonium carbamate. The conductive member according to any one of 3).
(5) The copper ion is from copper hydroxide, copper nitrate, nitrite, copper acetate, copper formate, copper citrate, copper oxalate, copper gluconate, copper benzoate, copper tartrate, copper oleate, copper acetylacetone The conductive member according to any one of (1) to (4), wherein the conductive member is obtained from one or more selected types.
(6) The dispersant is one or more selected from polyvinyl pyrrolidone, polyethyleneimine, polyacrylic acid, carboxymethylcellulose, polyacrylamide, polyvinyl alcohol, polyethylene glycol, polyethylene oxide, starch, and gelatin. The conductive member according to any one of (1) to (5), wherein the conductive member is an organic compound.
(7) The conductive member according to any one of (1) to (6), wherein the amount of the dispersant added is 0.1 to 500 parts by weight with respect to 100 parts by weight of copper ions. .
(8) After the copper fine particle-dispersed aqueous solution disposed on the base material is recovered from the copper fine particle-dispersed aqueous solution after the reduction reaction by centrifugal separation, filtration, squeezing separation, flotation separation, or sedimentation separation, It is a copper fine particle-dispersed aqueous solution obtained by dispersing the recovered copper fine particles in an alkaline aqueous solution having a pH in the range of 9 to 14. The conductive material according to any one of (1) to (7), Element.
(9)前記基材上に配置される銅微粒子分散水溶液に、炭素数が3〜8のアルコール、分子中に2以上の水酸基を有する多価アルコール、アルカノールアミンから選択される1種又は二種以上からなる有機溶媒が1〜30質量%含まれていることを特徴とする、前記(1)ないし(8)のいずれかに記載の導電部材。
(10)前記炭素数が3〜8のアルコールが1−プロパノール、2−プロパノール、2−ブタノール、2−メチル2−プロパノールから選択された1種又は2種以上であり、
前記分子中に2以上の水酸基を有する多価アルコールが、エチレングリコ−ル、ジエチレングリコ−ル、1,2−プロパンジオ−ル、1,3−プロパンジオ−ル、1,2−ブタンジオ−ル、1,3−ブタンジオ−ル、1,4−ブタンジオ−ル、2−ブテン−1,4−ジオール、2,3−ブタンジオ−ル、ペンタンジオ−ル、ヘキサンジオ−ル、オクタンジオ−ル、グリセロール、1,1,1−トリスヒドロキシメチルエタン、2−エチル−2−ヒドロキシメチル−1,3−プロパンジオール、1,2,6−ヘキサントリオール、1,2
,3−ヘキサントリオール、1,2,4−ブタントリオール、グリセロ−ル、トレイトレイトール、エリトリト−ル、ペンタエリスリト−ル、ペンチト−ル、キシリトール、リビトール、アラビトール、ヘキシト−ル、マンニトール、ソルビトール、ズルシトール、グリセリンアルデ、ジオキシアセトン、トレオース、エリトルロース、エリトロース、アラビノース、リボース、リブロース、キシロース、キシルロース、リキソース、グルコ−ス、フルクト−ス、マンノース、イドース、ソルボース、グロース、タロース、タガトース、ガラクトース、アロース、アルトロース、ラクト−ス、キシロ−ス、アラビノ−ス、イソマルト−ス、グルコヘプト−ス、ヘプト−ス、マルトトリオース、ラクツロース、及びトレハロースの中から選択される1種又は2種以上であり、
並びに、前記アルカノールアミンが、ジメタノールアミン、トリメタノールアミン、ジエタノールアミン、トリエタノールアミン、ジイソプロパノールアミン、トリイソプロパノールアミン、N−メチルジエタノールアミン、N−エチルジエタノールアミン、及びN−n−ブチルジエタノールアミンの中から選択される1種又は2種以上である、前記(9)に記載の導電部材。
(11)前記基材上に配置される銅微粒子分散水溶液が、前記(1)ないし(7)のいずれかで得られた銅微粒子分散水溶液に超音波照射、逆浸透膜によるろ過、限外ろ過膜によるろ過、真空脱水、又は凍結乾燥により、該銅微粒子分散水溶液中の水分を除去して得られる、水溶液中の銅微粒子濃度が1〜60質量%の分散水溶液であることを特徴とする、前記(1)ないし(7)のいずれか1項に記載の導電部材。
(12)前記基材上に配置される銅微粒子分散水溶液が、前記前記(9)又(10)で得られた銅微粒子分散水溶液に超音波照射、逆浸透膜によるろ過、限外ろ過膜によるろ過、真空脱水、又は凍結乾燥により、該銅微粒子分散水溶液に存在する水分と、炭素数が3〜8のアルコール、分子中に2以上の水酸基を有する多価アルコール、アルカノールアミンから選択される1種又は二種以上の一部を除去して得られる、水溶液中の銅微粒子濃度が1〜60質量%の分散水溶液であることを特徴とする、前記(9)又(10)に記載の導電部材。
(9) One or two kinds selected from alcohols having 3 to 8 carbon atoms, polyhydric alcohols having two or more hydroxyl groups in the molecule, and alkanolamines in the aqueous solution of copper fine particles disposed on the substrate. The conductive member according to any one of (1) to (8), wherein 1 to 30% by mass of the organic solvent is contained.
(10) The alcohol having 3 to 8 carbon atoms is one or more selected from 1-propanol, 2-propanol, 2-butanol, 2-methyl 2-propanol,
The polyhydric alcohol having two or more hydroxyl groups in the molecule is ethylene glycol, diethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2-butene-1,4-diol, 2,3-butanediol, pentanediol, hexanediol, octanediol, glycerol, 1, 1,1-trishydroxymethylethane, 2-ethyl-2-hydroxymethyl-1,3-propanediol, 1,2,6-hexanetriol, 1,2
, 3-hexanetriol, 1,2,4-butanetriol, glycerol, trayolitol, erythritol, pentaerythritol, pentitol, xylitol, ribitol, arabitol, hexitol, mannitol, sorbitol , Dulcitol, glycerin alde, dioxyacetone, threose, erythrulose, erythrose, arabinose, ribose, ribulose, xylose, xylulose, lyxose, glucose, fructose, mannose, idose, sorbose, growth, talose, tagatose, galactose, Selected from allose, altrose, lactose, xylose, arabinose, isomaltose, glucoheptose, heptose, maltotriose, lactulose, and trehalose It is one or two or more that,
And the alkanolamine is selected from dimethanolamine, trimethanolamine, diethanolamine, triethanolamine, diisopropanolamine, triisopropanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, and Nn-butyldiethanolamine. The conductive member according to (9), wherein the conductive member is one type or two or more types.
(11) The copper fine particle dispersed aqueous solution disposed on the base material is subjected to ultrasonic irradiation, filtration with a reverse osmosis membrane, ultrafiltration on the copper fine particle dispersed aqueous solution obtained in any one of (1) to (7). filtration by membrane, vacuum dehydration, or by lyophilization, obtained by removing the water of the copper fine particle dispersion aqueous solution, copper particle concentration in the aqueous solution, characterized in that 1 to 60 wt% of the aqueous dispersion The conductive member according to any one of (1) to (7).
(12) The copper fine particle dispersed aqueous solution disposed on the substrate is subjected to ultrasonic irradiation, filtration with a reverse osmosis membrane, ultrafiltration membrane on the copper fine particle dispersed aqueous solution obtained in the above (9) or (10). 1 selected from water present in the copper fine particle dispersed aqueous solution, alcohol having 3 to 8 carbon atoms, polyhydric alcohol having two or more hydroxyl groups in the molecule, and alkanolamine by filtration, vacuum dehydration, or freeze drying. The conductive material according to (9) or (10), wherein the conductive fine particle concentration is a dispersed aqueous solution having a copper fine particle concentration in an aqueous solution of 1 to 60% by mass obtained by removing a part of seeds or two or more species. Element.
本発明の導電部材は、少なくとも表面の一部が分散剤で覆われた分散性の高い銅微粒子の分散水溶液を基材上に配置して、乾燥後に焼成して形成される。
本発明において、還元反応はpHが9.2以上に保たれるので、銅イオンの酸化反応によるCu2O及びCuOの生成が抑制され、更に還元反応系において銅元素、並びに、炭素原子、水素原子、酸素原子、及び窒素原子以外の原子を含む化合物は添加されないので、得られる銅微粒子分散水溶液を基材上に配置して乾燥後、250℃以下の比較的低温で焼成しても導電性に優れ、不純物の少ない導電部材を得ることができる。更に、焼成の際に水素ガス等の還元性雰囲気下を必ずしも必要とせず、不活性ガス雰囲気下で焼成を行うことが可能である。
The conductive member of the present invention is formed by disposing a dispersed aqueous solution of copper fine particles having a high dispersibility, at least a part of the surface of which is covered with a dispersing agent, on a base material and firing after drying.
In the present invention, since the pH of the reduction reaction is maintained at 9.2 or higher, the production of Cu 2 O and CuO due to the oxidation reaction of copper ions is suppressed, and further, in the reduction reaction system, copper element, carbon atom, hydrogen Since compounds containing atoms other than atoms, oxygen atoms, and nitrogen atoms are not added, the resulting copper fine particle-dispersed aqueous solution is placed on a substrate, dried, and conductive even when fired at a relatively low temperature of 250 ° C. or lower. And a conductive member with few impurities can be obtained. Furthermore, it is not always necessary to have a reducing atmosphere such as hydrogen gas during firing, and firing can be performed in an inert gas atmosphere.
〔1〕「導電部材」について
本発明の「導電部材」は、一次粒子の平均粒径1〜150nmの銅微粒子が少なくともその表面の一部が分散剤で覆われて水溶液中に分散されている、銅微粒子分散水溶液であって、
(i)銅イオンを、分散剤の存在下でpH調整剤によりpH9.2以上に調整したアンモニア水溶液中でアンモニアと下記反応をさせ、水溶性の銅アンミン錯体を得る工程(工程1)、
Cu2++4NH3 → [Cu(NH3)4]2+
又は Cu2++4NH4(OH) → [Cu(NH3)4]2+ +4H2O
(ii)前記工程1で得られた銅アンミン錯体を含む還元反応水溶液において、下記の銅アンミン錯体の電解還元反応により、少なくとも表面の一部が分散剤で覆われた銅微粒子を形成する工程(工程2)、
Cu(NH3)4 2++2e− → Cu+2NH3
又は Cu(NH3)4 2++2e−+2H2O→ Cu+2NH4(OH)
を含み、前記還元反応の系において、銅元素、炭素原子、水素原子、酸素原子、及び窒素原子以外の原子を含む化合物を含まずに製造された銅微粒子分散水溶液を基材上に配置して、乾燥後に焼成して形成されたことを特徴とする。
[1] About “Conductive Member” In the “conductive member” of the present invention, copper fine particles having an average primary particle diameter of 1 to 150 nm are dispersed in an aqueous solution with at least a part of the surface covered with a dispersant. A copper fine particle dispersed aqueous solution,
(I) a step of obtaining a water-soluble copper ammine complex by reacting copper ions with ammonia in an aqueous ammonia solution adjusted to a pH of 9.2 or more with a pH adjuster in the presence of a dispersant (step 1);
Cu 2+ + 4NH 3 → [Cu (NH 3 ) 4 ] 2+
Or Cu 2+ + 4NH 4 (OH) → [Cu (NH 3 ) 4 ] 2+ + 4H 2 O
(Ii) In the reduction reaction aqueous solution containing the copper ammine complex obtained in the step 1, the step of forming copper fine particles in which at least a part of the surface is covered with the dispersant by the electrolytic reduction reaction of the following copper ammine complex ( Step 2),
Cu (NH 3 ) 4 2+ + 2e − → Cu + 2NH 3
Or Cu (NH 3 ) 4 2+ + 2e − + 2H 2 O → Cu + 2NH 4 (OH)
In the reduction reaction system, a copper fine particle dispersed aqueous solution produced without containing a compound containing an element other than a copper element, a carbon atom, a hydrogen atom, an oxygen atom, and a nitrogen atom is disposed on a substrate. It is characterized by being formed by baking after drying.
(1)銅微粒子、分散剤、及び銅微粒子分散水溶液
(イ)銅微粒子
本発明の「導電部材」を形成する銅微粒子分散水溶液中の銅微粒子は、一次粒子の平均粒径1〜150nmの微粒子である。
ここで、一次粒子の平均粒径とは、二次粒子を構成する銅微粒子の一次粒子の直径の意味である。該一次粒子径は、透過電子顕微鏡(TEM)を用いて測定することができる。また、平均粒径とは、一次粒子の数平均粒径を意味する。微粒子の一次粒子の平均粒径は、1〜150nmであるが、製造と取り扱い等の実用的な面からは、1〜100nmの微粒子が好ましい。
(1) Copper fine particles, dispersant, and copper fine particle dispersed aqueous solution (a) Copper fine particles The copper fine particles in the copper fine particle dispersed aqueous solution forming the “conductive member” of the present invention are fine particles having an average primary particle diameter of 1 to 150 nm. It is.
Here, the average particle size of the primary particles means the diameter of the primary particles of the copper fine particles constituting the secondary particles. The primary particle diameter can be measured using a transmission electron microscope (TEM). Moreover, an average particle diameter means the number average particle diameter of a primary particle. The average primary particle size of the fine particles is 1 to 150 nm, but from a practical aspect such as production and handling, fine particles of 1 to 100 nm are preferable.
(ロ)分散水溶液における銅微粒子の分散
本発明において、分散水溶液における銅微粒子は少なくともその表面の一部が分散剤に覆われた状態で水溶液中に分散している。分散剤は、水溶液中で銅微粒子の凝集を防止して分散性を良好に維持する作用を有する。尚、この場合の「分散剤が銅微粒子の表面を覆うように存在」における「覆う」は、当該技術分野において、「被覆され」、「囲まれた」、「保護された」等の記載表現が使用されることもある。
また、上記「分散剤が銅微粒子の表面を覆う」とは、銅微粒子の全表面が分散剤で覆われていなくとも、その一部が覆われていても分散効果は顕著に発揮される。
このような分散剤が銅微粒子を分散させるメカニズムは完全に解明されてはいないが、例えば分散剤に存在する官能基の非共有電子対を有する原子部分が銅微粒子の表面に吸着して、分子層を形成し、互いに銅微粒子同士の接近をさせない、斥力が発生していることが予想される。
(B) Dispersion of Copper Fine Particles in Dispersed Aqueous Solution In the present invention, the copper fine particles in the dispersed aqueous solution are dispersed in the aqueous solution with at least a part of the surface thereof being covered with the dispersant. The dispersant has an action of preventing the aggregation of copper fine particles in an aqueous solution and maintaining good dispersibility. In this case, “covering” in “the dispersing agent is present so as to cover the surface of the copper fine particles” is described in the technical field as “coated”, “enclosed”, “protected”, etc. May be used.
In addition, the above “dispersing agent covers the surface of the copper fine particles” means that the dispersion effect is remarkably exhibited even if the entire surface of the copper fine particles is not covered with the dispersing agent but part of it is covered.
The mechanism by which such a dispersing agent disperses the copper fine particles has not been completely elucidated, but for example, an atomic part having an unshared electron pair of a functional group present in the dispersing agent is adsorbed on the surface of the copper fine particles, and the molecules It is expected that repulsive force is generated that forms a layer and does not allow copper fine particles to approach each other.
(ハ)分散剤
本発明において、還元反応により銅微粒子を形成する際に、分散剤を使用する。
分散剤は、水に対して溶解性を有していると共に、反応系中で析出した銅微粒子の少なくともその表面の一部を覆うように存在して、銅微粒子の凝集を防止して分散性を良好に維持する作用を有する。本発明の分散剤は上記作用を有し、かつ水溶液中で上記作用を奏するものであれば、特に制限されるものではない。
分散剤としては、その化学構造にもよるが数平均分子量が100〜100,000程度の、水に対して溶解性を有し、かつ水溶液で銅イオンから還元反応で析出した銅微粒子を良好に分散させることが可能なもので、かつ炭素原子、水素原子、酸素原子、及び窒素原子から選択された2種以上の原子からなる化合物(高分子化合物も含む)の分散剤であればいずれも使用可能である。
(C) Dispersant In the present invention, a dispersant is used when forming copper fine particles by a reduction reaction.
The dispersant is soluble in water and is present so as to cover at least part of the surface of the copper fine particles precipitated in the reaction system, thereby preventing the copper fine particles from aggregating and dispersing. Has the effect of maintaining good. The dispersant of the present invention is not particularly limited as long as it has the above action and exhibits the above action in an aqueous solution.
As a dispersing agent, although depending on the chemical structure, the number average molecular weight is about 100 to 100,000, which is soluble in water, and is excellent in copper fine particles precipitated by reduction reaction from copper ions in an aqueous solution. Any dispersant that can be dispersed and is a compound (including a polymer compound) composed of two or more atoms selected from a carbon atom, a hydrogen atom, an oxygen atom, and a nitrogen atom is used. Is possible.
上記分散剤として好ましいのは、ポリビニルピロリドン、ポリエチレンイミン等のアミン系の高分子;ポリアクリル酸、カルボキシメチルセルロース等のカルボン酸基を有する炭化水素系高分子;ポリアクリルアミド等のアクリルアミド;ポリビニルアルコール、ポリエチレンオキシド、更にはデンプン、及びゼラチンの中から選択される1種又は2種以上である。
上記例示した分散剤の具体例として、ポリビニルピロリドン(分子量:1000〜500,000)、ポリエチレンイミン(分子量:100〜100,000)、カルボキシメチルセルロース(アルカリセルロースのヒドロキシル基Na塩のカルボキシメチル基への置換度:0.4以上、分子量:1000〜100,000)、ポリアクリルアミド(分子量:100〜6,000,000)、ポリビニルアルコール(分子量:1000〜100,000)、ポリエチレングリコール(分子量:100〜50,000)、ポリエチレンオキシド(分子量:50,000〜900,000)、ゼラチン(平均分子量:61,000〜67,000)、水溶性のデンプン等が挙げられる。
The dispersant is preferably an amine polymer such as polyvinylpyrrolidone or polyethyleneimine; a hydrocarbon polymer having a carboxylic acid group such as polyacrylic acid or carboxymethylcellulose; an acrylamide such as polyacrylamide; One or more selected from ethylene oxide, starch, and gelatin.
Specific examples of the dispersant exemplified above include polyvinylpyrrolidone (molecular weight: 1000 to 500,000), polyethyleneimine (molecular weight: 100 to 100,000), carboxymethylcellulose (alkalicellulose hydroxyl group Na salt to carboxymethyl group) Degree of substitution: 0.4 or more, molecular weight: 1000 to 100,000, polyacrylamide (molecular weight: 100 to 6,000,000), polyvinyl alcohol (molecular weight: 1000 to 100,000), polyethylene glycol (molecular weight: 100 to 100) 50,000), polyethylene oxide (molecular weight: 50,000 to 900,000), gelatin (average molecular weight: 61,000 to 67,000), water-soluble starch and the like.
上記かっこ内にそれぞれの分散剤の数平均分子量を示すが、このような分子量範囲にあるものは水溶性を有するので、本発明において好適に使用できる。尚、これらの2種以上を混合して使用することもできる。
また、分散剤の添加量は、還元反応水溶液から生成する銅微粒子の濃度にもよるが、該銅原子100重量部に対して、0.1〜500重量部が好ましく、0.5〜100重量部がより好ましい。分散剤の添加量が前記0.1未満では凝集を抑制する効果が十分に得られない場合があり、一方、前記500重量部を超える場合には、分散上に支障がなくとも、銅微粒子分散水溶液を塗布後、乾燥・焼成時に、過剰の分散剤が、銅微粒子の焼結を阻害して、膜質の緻密さを低下させる場合があると共に、分散剤の焼成残渣が、金属被膜中に残存して、導電性を低下させるおそれがある。
The number average molecular weights of the respective dispersants are shown in the parentheses, but those having such a molecular weight range are water-soluble, and can be suitably used in the present invention. In addition, these 2 or more types can also be mixed and used.
Moreover, although the addition amount of a dispersing agent is based also on the density | concentration of the copper fine particle produced | generated from reduction reaction aqueous solution, 0.1-500 weight part is preferable with respect to 100 weight part of this copper atom, 0.5-100 weight Part is more preferred. If the added amount of the dispersant is less than 0.1, the effect of suppressing aggregation may not be sufficiently obtained. On the other hand, if it exceeds 500 parts by weight, the copper fine particles are dispersed even if there is no problem in dispersion. After applying an aqueous solution, during drying and firing, an excessive dispersant may inhibit the sintering of the copper fine particles and reduce the density of the film quality, and the firing residue of the dispersant remains in the metal film. As a result, the conductivity may be reduced.
尚、銅微粒子分散水溶液中において前記分散剤と生成した銅微粒子の重量比が(分散剤/銅微粒子)0.001〜5の範囲であることが好ましい。この重量比については、銅微粒子分散水溶液から、分散剤で覆われた銅微粒子を遠心分離等の操作により回収して定量分析により、確認することが可能である。
その具体的例として、銅微粒子分散水溶液をサンプリングして、遠心分離操作により分散剤で覆われた銅微粒子を分析用サンプルとして回収し、酸化性の溶液中で、分散剤が反応しない条件下で銅微粒子を溶解した溶液を調製し、該溶液を液体クロマトグラフィー等により定量分析すれば、重量比(分散剤/銅微粒子)を測定することができる。
また、前記銅微粒子分析用サンプルを、銅微粒子から分散剤を溶剤中に抽出した後に、必要がある場合には蒸発等の濃縮操作を行い、液体クロマトグラフィー、又は分散剤中の特定の元素(窒素、イオウ等)をX線光電子分光(XPS(X-ray Photoelectron Spectroscopy))、オージェ電子分光分析(AES(Auger Electron Spectroscopy))等の分析により、重量比(分散剤/銅微粒子)の測定を行うことが可能である。
In addition, it is preferable that the weight ratio of the said dispersing agent and the produced | generated copper fine particle in the copper fine particle dispersion aqueous solution is the range of (dispersant / copper fine particle) 0.001-5. This weight ratio can be confirmed by recovering the copper fine particles covered with the dispersant from the aqueous copper fine particle dispersion by an operation such as centrifugation and quantitative analysis.
As a specific example, a copper fine particle-dispersed aqueous solution is sampled, and copper fine particles covered with a dispersant are collected as a sample for analysis by centrifugal separation. Under conditions where the dispersant does not react in an oxidizing solution. If a solution in which copper fine particles are dissolved is prepared and the solution is quantitatively analyzed by liquid chromatography or the like, the weight ratio (dispersant / copper fine particles) can be measured.
Moreover, after extracting the dispersing agent from the copper fine particles into the solvent, the copper fine particle analysis sample is subjected to a concentration operation such as evaporation if necessary, and subjected to liquid chromatography or a specific element ( Measurement of weight ratio (dispersant / copper fine particles) by X-ray photoelectron spectroscopy (XPS), Auger electron spectroscopy (AES), etc. Is possible.
(ニ)銅微粒子分散水溶液
前記銅微粒子分散水溶液には、炭素数が3〜8のアルコール、分子中に2以上の水酸基を有する多価アルコール、アルカノールアミンから選択される1種又は二種以上からなる有機溶媒を0〜30質量%含有させることができる。
銅微粒子分散水溶液にこのような有機溶媒が含有されていると、該銅微粒子分散水溶液をそのまま又は濃縮後にパターニングして焼成する際に還元作用を発揮するので、電気抵抗値の低い焼結体を得ることができる。
尚、「炭素数が3〜8のアルコール、分子中に2以上の水酸基を有する多価アルコール、アルカノールアミンから選択される1種又は二種以上からなる有機溶媒」は、還元反応開始前に還元反応水溶液に添加されていてもよく、還元反応終了後に分散水溶液(還元反応終了後に銅微粒子分散水溶液から銅微粒子を回収し、その後該銅微粒子を分散する分散水溶液を含む)に添加されていてもよく、又、還元反応終了後に分散水溶液の一部を除去して銅微粒子濃度が高められた分散水溶液に添加されていてもよい。
前記炭素数が3〜8のアルコールは、1−プロパノール、2−プロパノール、2−ブタノール、2−メチル2−プロパノールから選択された1種又は2種以上が例示でき、
分子中に2以上の水酸基を有する多価アルコールは、エチレングリコ−ル、ジエチレングリコ−ル、1,2−プロパンジオ−ル、1,3−プロパンジオ−ル、1,2−ブタンジオ−ル、1,3−ブタンジオ−ル、1,4−ブタンジオ−ル、2−ブテン−1,4−ジオール、2,3−ブタンジオ−ル、ペンタンジオ−ル、ヘキサンジオ−ル、オクタンジオ−ル、グリセロール、1,1,1−トリスヒドロキシメチルエタン、2−エチル−2−ヒドロキシメチル−1,3−プロパンジオール、1,2,6−ヘキサントリオール、1,2,3−ヘキサントリオール、1,2,4−ブタントリオール、グリセロ−ル、トレイトレイトール、エリトリト−ル、ペンタエリスリト−ル、ペンチト−ル、キシリトール、リビトール、アラビトール、ヘキシト−ル、マンニトール、ソルビトール、ズルシトール、グリセリンアルデ、ジオキシアセトン、トレオース、エリトルロース、エリトロース、アラビノース、リボース、リブロース、キシロース、キシルロース、リキソース、グルコ−ス、フルクト−ス、マンノース、イドース、ソルボース、グロース、タロース、タガトース、ガラクトース、アロース、アルトロース、ラクト−ス、アラビノ−ス、イソマルト−ス、グルコヘプト−ス、ヘプト−ス、マルトトリオース、ラクツロース、及びトレハロースの中から選択される1種又は2種以上が例示でき、
並びに、アルカノールアミンは、ジメタノールアミン、トリメタノールアミン、ジエタノールアミン、トリエタノールアミン、ジイソプロパノールアミン、トリイソプロパノールアミン、N−メチルジエタノールアミン、N−エチルジエタノールアミン、及びN−n−ブチルジエタノールアミンの中から選択される1種又は2種以上が例示できる。
(D) Copper fine particle-dispersed aqueous solution The copper fine particle-dispersed aqueous solution includes one or more selected from alcohols having 3 to 8 carbon atoms, polyhydric alcohols having two or more hydroxyl groups in the molecule, and alkanolamines. 0-30 mass% of organic solvents can be contained.
When such an organic solvent is contained in the copper fine particle dispersed aqueous solution, the copper fine particle dispersed aqueous solution exhibits a reducing action when it is patterned and baked as it is or after concentration. Can be obtained.
In addition, “an organic solvent comprising one or two or more alcohols selected from alcohols having 3 to 8 carbon atoms, polyhydric alcohols having two or more hydroxyl groups in the molecule, and alkanolamines” are reduced before the start of the reduction reaction. It may be added to a reaction aqueous solution, or may be added to a dispersion aqueous solution after completion of the reduction reaction (including a dispersion aqueous solution in which copper fine particles are recovered from the copper fine particle dispersion aqueous solution after the reduction reaction is completed and then dispersed). Alternatively, after completion of the reduction reaction, a part of the dispersed aqueous solution may be removed and added to the dispersed aqueous solution in which the copper fine particle concentration is increased.
Examples of the alcohol having 3 to 8 carbon atoms include one or more selected from 1-propanol, 2-propanol, 2-butanol, and 2-methyl 2-propanol,
Polyhydric alcohols having two or more hydroxyl groups in the molecule are ethylene glycol, diethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, , 3-butanediol, 1,4-butanediol, 2-butene-1,4-diol, 2,3-butanediol, pentanediol, hexanediol, octanediol, glycerol, 1,1 , 1-trishydroxymethylethane, 2-ethyl-2-hydroxymethyl-1,3-propanediol, 1,2,6-hexanetriol, 1,2,3-hexanetriol, 1,2,4-butanetriol Glycerol, tray tray, erythritol, pentaerythritol, pentitol, xylitol, ribitol, arabitol, hexite Mannitol, sorbitol, dulcitol, glycerine alde, dioxyacetone, threose, erythrulose, erythrose, arabinose, ribose, ribulose, xylose, xylulose, lyxose, glucose, fructose, mannose, idose, sorbose, growth, talose , Tagatose, galactose, allose, altrose, lactose, arabinose, isomaltose, glucoheptose, heptose, maltotriose, lactulose, and trehalose Can be illustrated,
And the alkanolamine is selected from dimethanolamine, trimethanolamine, diethanolamine, triethanolamine, diisopropanolamine, triisopropanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, and Nn-butyldiethanolamine. 1 type or 2 types or more can be illustrated.
(2)工程1
工程1は、銅イオンを分散剤の存在下で、pH調整剤によりpH9.2以上に調整したアンモニア水溶液中でアンモニアとの下記反応により、水溶性の銅アンミン錯体を得る工程である。
Cu2++4NH3 → [Cu(NH3)4]2+
又は Cu2++4NH4(OH) → [Cu(NH3)4]2+ +4H2O
(イ)銅イオン
工程1で使用する「銅イオン」を形成する化合物は、銅元素、並びに炭素原子、水素原子、酸素原子、及び窒素原子から選択された2種以上の原子からなる化合物であり、具体的には水酸化銅、硝酸銅、亜硝酸塩、酢酸銅、蟻酸銅、クエン酸銅、しゅう酸銅、グルコン酸銅、安息香酸銅、酒石酸銅、オレイン酸銅、アセチルアセトン銅から選択された1種又は2種以上の使用が好ましい。
(ロ)pH調整剤
工程1で使用するpH調整剤は、炭素原子、水素原子、酸素原子、及び窒素原子から選択された2種以上の原子からなる化合物が好ましく、このような化合物として、具体的には酢酸アンモニウム、炭酸アンモニウム、蟻酸アンモニウム、プロピオンアンモニウム、炭酸水素アンモニウム、シュウ酸アンモニウム、カルバミン酸アンモニウムから選択された1種又は2種以上の使用が好ましい。
(2) Step 1
Step 1 is a step of obtaining a water-soluble copper ammine complex by the following reaction with ammonia in an aqueous ammonia solution adjusted to pH 9.2 or higher with a pH adjuster in the presence of a dispersant.
Cu 2+ + 4NH 3 → [Cu (NH 3 ) 4 ] 2+
Or Cu 2+ + 4NH 4 (OH) → [Cu (NH 3 ) 4 ] 2+ + 4H 2 O
(B) The compound that forms the “copper ion” used in the copper ion step 1 is a compound composed of a copper element and two or more atoms selected from a carbon atom, a hydrogen atom, an oxygen atom, and a nitrogen atom. , Specifically selected from copper hydroxide, copper nitrate, nitrite, copper acetate, copper formate, copper citrate, copper oxalate, copper gluconate, copper benzoate, copper tartrate, copper oleate, copper acetylacetone One or more types are preferably used.
(B) pH adjuster The pH adjuster used in Step 1 is preferably a compound composed of two or more atoms selected from a carbon atom, a hydrogen atom, an oxygen atom, and a nitrogen atom. Specifically, it is preferable to use one or more selected from ammonium acetate, ammonium carbonate, ammonium formate, ammonium propionate, ammonium hydrogen carbonate, ammonium oxalate, and ammonium carbamate.
(ハ)工程1における銅アンミン錯体の生成
銅イオンを分散剤の存在下、アンモニア水溶液中でアンモニア(又は水酸化アンモニウム)との上記反応により、水溶性の銅アンミン錯体を得る場合に、pH調整剤によりpH9.2以上に調整される。このようなアルカリ性の水溶液においては酸化反応が抑制されて銅原子にアンモニアイオンが配位し、水溶性の銅アンミン錯体が形成される。
この場合、pHは9.2以上が好ましく、11以上が更に好ましい。
pHが9.2未満であると、水酸化物イオン(OH−)濃度が低くなる結果、銅アンミン錯体が生成しづらくなり、また銅微粒子表面での酸化反応が進行し易くなる結果、酸化銅が形成されるので好ましくない。
工程1における反応は、アンモニアが溶解している、pHが調整された水溶液に、前記銅イオンを含む水溶液を連続的に滴下してもよく、一度に添加してもよい。
前記銅イオンを含む水溶液中の好ましい銅イオン濃度は、実用上0.01〜1モル/L(リットル)程度であり、アンモニアが溶解している水溶液中の好ましいアンモニア濃度は0.0001〜10モル/L程度である。
(C) Formation of a copper ammine complex in step 1 When obtaining a water-soluble copper ammine complex by the above reaction with ammonia (or ammonium hydroxide) in an aqueous ammonia solution in the presence of a dispersing agent, adjust the pH. The pH is adjusted to 9.2 or higher with an agent. In such an alkaline aqueous solution, the oxidation reaction is suppressed, and ammonia ions are coordinated to the copper atom to form a water-soluble copper ammine complex.
In this case, the pH is preferably 9.2 or more, and more preferably 11 or more.
If the pH is less than 9.2, the hydroxide ion (OH − ) concentration becomes low, so that it becomes difficult to form a copper ammine complex, and the oxidation reaction on the surface of the copper fine particles tends to proceed. Is not preferable.
In the reaction in Step 1, the aqueous solution containing copper ions may be continuously dropped into an aqueous solution in which ammonia is dissolved and the pH is adjusted, or may be added at once.
The preferable copper ion concentration in the aqueous solution containing copper ions is practically about 0.01 to 1 mol / L (liter), and the preferable ammonia concentration in the aqueous solution in which ammonia is dissolved is 0.0001 to 10 mol. / L or so.
(3)工程2
工程2は、前記銅アンミン錯体を、電解還元により下記の還元反応により、分散水溶液中で少なくとも表面の一部が分散剤で覆われた状態で銅微粒子を形成する工程である。
Cu(NH3)4 2++2e− → Cu+2NH3
又は Cu(NH3)4 2++2e−+2H2O→ Cu+2NH4(OH)
すなわち、工程1で形成された銅アンミン錯体が溶解している水溶液中に電極を存在させて、電解還元反応により銅微粒子を形成する工程である。還元反応により生成した一次粒子の粒子径が1〜150nm程度の銅微粒子は、分散剤の作用により、二次凝集が抑制されて水溶液中に均一に分散される。
(イ)電極(陽極と陰極)材料等
極は、白金、カーボン等が好ましく、陽極は、Cu、Cu−Sn合金、カーボン、白金等が好ましい。尚、陰極表面付近に析出した粒子を脱離、回収するために陰極に超音波振動等の揺動を与えることが可能な構造とすることもできる。
(3) Step 2
Step 2, the copper ammine complex, by a reduction reaction of the following by electrolytic reduction, at least a portion of the surface with the dispersion water solution is a step of forming a copper fine particles in a state covered with the dispersant.
Cu (NH 3 ) 4 2+ + 2e − → Cu + 2NH 3
Or Cu (NH 3 ) 4 2+ + 2e − + 2H 2 O → Cu + 2NH 4 (OH)
That is, the electrode is present in the aqueous solution in which the copper ammine complex formed in step 1 is dissolved, and copper fine particles are formed by an electrolytic reduction reaction. The copper fine particles having a primary particle size of about 1 to 150 nm generated by the reduction reaction are uniformly dispersed in the aqueous solution with the secondary aggregation suppressed by the action of the dispersant.
(A) Electrode (Anode and Cathode) Material, etc. The electrode is preferably platinum or carbon, and the anode is preferably Cu, Cu—Sn alloy, carbon, platinum or the like. In addition, in order to desorb and collect particles deposited in the vicinity of the cathode surface, it is possible to adopt a structure capable of imparting oscillation such as ultrasonic vibration to the cathode.
(ロ)電解還元反応
電解還元反応のpHは、好ましくは9〜14、より好ましくは9.5〜13.5の範囲に調整する。pHが9未満では還元反応による銅が析出するのを妨げるなどの悪影響を与える場合があり、pHが14を超えると電流密度範囲が狭くなり、電流効率が低下する場合がある。
電流密度は好ましくは0.3〜10A/dm2 、より好ましくは0.5〜6A/dm2 程度である。還元温度は、10〜70℃が好ましく、高温になるほど還元反応速度は速くなり、低温になるほど析出する粒子の粒径は小さくなる傾向がある。
尚、銅微粒子の一次粒子の平均粒径の制御は、銅イオン、分散剤等の選択、及び電流、電圧、還元温度、時間、pH等の調整により行うことが可能である。
(B) Electrolytic reduction reaction The pH of the electrolytic reduction reaction is preferably adjusted to the range of 9 to 14, more preferably 9.5 to 13.5. If the pH is less than 9, there may be adverse effects such as preventing the copper from being precipitated by the reduction reaction. If the pH exceeds 14, the current density range may be narrowed and the current efficiency may be reduced.
The current density is preferably about 0.3 to 10 A / dm 2 , more preferably about 0.5 to 6 A / dm 2 . The reduction temperature is preferably 10 to 70 ° C., the higher the temperature, the faster the reduction reaction rate, and the lower the temperature, the smaller the particle size of the precipitated particles.
The average particle size of the primary particles of the copper fine particles can be controlled by selecting copper ions, a dispersant, etc., and adjusting the current, voltage, reduction temperature, time, pH, and the like.
(ハ)還元反応水溶液から銅微粒子を回収後、該銅微粒子分散水溶液への分散
還元反応水溶液中には未反応の銅イオンが残存する場合があるので、未還元銅イオンを銅微粒子分散水溶液中に存在させたくない場合、以下の方法により銅イオンが除去された銅微粒子分散水溶液を得ることができる。
電解還元反応終了後に、電極表面に付着した銅微粒子を電極から脱離・回収する。該脱離方法としては、電極の洗浄、電極に逆電流を流して電極表面に付着した銅微粒子の脱離、また上記したように陰極に超音波振動等の揺動を与える脱離等を行うことができる。
電極から脱離した銅微粒子を遠心分離、濾過、圧搾分離、浮上分離、又は沈降分離より回収した後、該回収した銅微粒子をpHが9〜14の範囲のアルカリ水溶液中に分散させて銅微粒子分散水溶液を得ることがきる。
尚、銅微粒子をpHが9〜14のアルカリ水溶液中に分散させるのは、該水溶液において銅微粒子の酸化反応を抑制するためである。
(C) After recovering copper fine particles from the reduction reaction aqueous solution, unreacted copper ions may remain in the dispersion reduction reaction aqueous solution to the copper fine particle dispersion aqueous solution. In the case where it is not desired to be present, an aqueous copper fine particle dispersion in which copper ions are removed can be obtained by the following method.
After the electrolytic reduction reaction is completed, the copper fine particles adhering to the electrode surface are desorbed and collected from the electrode. As the desorption method, cleaning of the electrode, desorption of the copper fine particles adhering to the electrode surface by applying a reverse current to the electrode, desorption which gives fluctuation such as ultrasonic vibration to the cathode as described above, etc. be able to.
After recovering the copper fine particles detached from the electrode by centrifugation, filtration, squeezing separation, flotation separation, or sedimentation separation, the recovered copper fine particles are dispersed in an alkaline aqueous solution having a pH of 9 to 14 to obtain copper fine particles. A dispersed aqueous solution can be obtained.
The reason why the copper fine particles are dispersed in the alkaline aqueous solution having a pH of 9 to 14 is to suppress the oxidation reaction of the copper fine particles in the aqueous solution.
(4)銅微粒子分散水溶液の撹拌による分散性の向上
かくして得られた銅微粒子分散水溶液中には、一次粒子の平均粒径1〜150nmの銅微粒子が少なくともその表面の一部が分散剤で覆われて水溶液中に、二次凝集性が少ない状態で分散されているが、更に撹拌して分散性を向上することが望ましい。
銅微粒子分散水溶液の撹拌方法としては、公知の撹拌方法を採用することができるが、超音波照射方法を採用するのが好ましい。
上記超音波照射時間は、特に制限はなく任意に選択することが可能である。例えば、超音波照射時間を5〜60分間の間で任意に設定すると照射時間が長い方が、平均二次凝集サイズが小さくなる傾向にある。
(4) Improvement of dispersibility by stirring of copper fine particle dispersed aqueous solution In the copper fine particle dispersed aqueous solution thus obtained, copper fine particles having an average particle size of 1 to 150 nm of primary particles are at least partially covered with a dispersant. Although it is dispersed in the aqueous solution in a state where the secondary cohesiveness is low, it is desirable to further improve the dispersibility by stirring.
As a stirring method for the copper fine particle-dispersed aqueous solution, a known stirring method can be adopted, but an ultrasonic irradiation method is preferably adopted.
The ultrasonic irradiation time is not particularly limited and can be arbitrarily selected. For example, when the ultrasonic irradiation time is arbitrarily set between 5 and 60 minutes, the longer the irradiation time, the smaller the average secondary aggregation size.
(5)銅微粒子分散水溶液の濃縮方法
上記工程2で得られた微粒子分散水溶液は必要に応じて、水分を除去することにより濃縮して、使用することができる。このような濃縮操作としては超音波照射、逆浸透膜、限外ろ過膜、真空脱水、及び凍結乾燥、更にこれらの2種以上の同時利用等の操作が挙げられる。
尚、前記銅微粒子分散水溶液に、炭素数が3〜8のアルコール、分子中に2以上の水酸基を有する多価アルコール、アルカノールアミンから選択される1種又は二種以上からなる有機溶媒が1〜30質量%含まれている場合には、水分を加熱除去する際に共沸現象を利用して、効率よく水分除去を行うことが可能になる。このような場合には、水分及び前記有機溶媒についても、前記濃縮操作によって、除去することが可能である。
このような濃縮操作により、水溶液中の銅微粒子濃度が0.01〜5質量%の分散水溶液中の水分の一部を除去して、水溶液中の銅微粒子濃度が1〜60質量%の分散水溶液を得ることが可能である。
(5) Concentration method of copper fine particle-dispersed aqueous solution The fine particle-dispersed aqueous solution obtained in the above step 2 can be used after being concentrated by removing water, if necessary. Examples of such a concentration operation include operations such as ultrasonic irradiation, reverse osmosis membrane, ultrafiltration membrane, vacuum dehydration, and lyophilization, and simultaneous use of two or more of these.
In addition, the organic solvent which consists of 1 type, or 2 or more types selected from the C3-C8 alcohol, the polyhydric alcohol which has a 2 or more hydroxyl group in a molecule | numerator, and an alkanolamine in the said copper fine particle dispersion | distribution aqueous solution is 1-. In the case where 30% by mass is contained, it is possible to efficiently remove moisture by using an azeotropic phenomenon when moisture is removed by heating. In such a case, moisture and the organic solvent can also be removed by the concentration operation.
By such a concentration operation, a part of the water in the dispersed aqueous solution having a copper fine particle concentration of 0.01 to 5% by mass in the aqueous solution is removed, and the dispersed water having a copper fine particle concentration in the aqueous solution of 1 to 60% by mass. It is possible to obtain a solution.
(6)導電部材
本発明の導電部材を形成する微粒子分散水溶液は、分散性と保存安定性に優れているので、インクジェット用インク、エッチングレジスト、ソルダーレジスト、誘電体パターン、電極(導体回路)パターン、電子部品の配線パターン、導電性ペースト、導電性インク、導電フィルム等に広く用いることができる。該銅微粒子分散水溶液を、例えば、インクジェット法等により基材上に配置して、乾燥後、焼成して金属含有薄膜又は金属含有細線等の導電部材を形成することができる。
前記銅微粒子分散水溶液を、従来よりも低い焼成温度、例えば250℃以下、更に220℃以下の比較的低温でも焼成することが可能となり、また、水素ガス等の還元性ガスを必ずしも使用する必要がなく、不活性ガス中における焼成を採用しても、導電性と基板密着性に優れる導電部材を形成することが可能となる。上記基材は特に制限はなく使用目的等により、ガラス、ポリイミド等が使用でき、乾燥と焼成は、アルゴン等の不活性ガス雰囲気下で行うことができる。
(6) Conductive member Since the fine particle dispersed aqueous solution forming the conductive member of the present invention is excellent in dispersibility and storage stability, ink for inkjet, etching resist, solder resist, dielectric pattern, electrode (conductor circuit) pattern It can be widely used for wiring patterns of electronic parts, conductive pastes, conductive inks, conductive films and the like. The copper fine particle-dispersed aqueous solution can be placed on a substrate by, for example, an ink jet method, dried, and fired to form a conductive member such as a metal-containing thin film or a metal-containing thin wire.
The copper fine particle-dispersed aqueous solution can be fired even at a relatively low firing temperature, for example, 250 ° C. or lower, and further 220 ° C. or lower, and a reducing gas such as hydrogen gas needs to be used. However, even if firing in an inert gas is employed, a conductive member having excellent conductivity and substrate adhesion can be formed. There is no restriction | limiting in particular in the said base material, Glass, a polyimide, etc. can be used by a use purpose etc., Drying and baking can be performed in inert gas atmosphere, such as argon.
〔2〕銅微粒子分散水溶液の保管
本発明の導電部材を形成する際に基材上に配置される銅微粒子分散水溶液は、銅微粒子分散水溶液が入った保管容器へ、乾燥状態の不活性ガスを充填して気密封止して保管することが望ましい。このことにより、銅微粒子分散水溶液中の銅が酸化するのを防ぎ、少なくとも3カ月間は保存安定性を確保することが出来る。
[2] Storage of copper fine particle dispersed aqueous solution The copper fine particle dispersed aqueous solution disposed on the base material when forming the conductive member of the present invention is supplied with dry inert gas in a storage container containing the copper fine particle dispersed aqueous solution. It is desirable to store it after filling and hermetically sealing. This prevents copper in the aqueous copper fine particle dispersion from being oxidized and ensures storage stability for at least 3 months.
次に、実施例により本発明をより具体的に説明する。尚、本発明はこれらの実施例に限定されるものではない。
[実施例1]
(1)銅微粒子分散水溶液の調製
水酸化銅(Cu(OH)2)0.2gを濃度0.5mol/Lのアンモニア水50mlに溶解させ、さらに0.5mol/Lの酢酸アンモニウムを添加してpHを10に調整し、銅アンミン錯体を含む溶液とした。次に、この溶液にポリビニルピロリドン0.5gを添加して攪拌溶解させた後、溶液中で白金板陰極(カソード電極)(片面16mm2)と白金板陽極(アノード電極)との間を25℃で1分間通電し還元反応を行った。この時、印加した電流密度は25mA/mm2以下とした。以上のようにして、銅微粒子が水溶液中に分散した銅微粒子分散水溶液を得た。
(2)銅微粒子分散水溶液の濃縮
この銅微粒子分散水溶液を、30℃において、1.6MHz、12Wの超音波を液面下から気相に向かって1時間照射して銅微粒子の濃縮を行い、銅微粒子濃度が10質量%の銅微粒子分散水溶液を得た。該銅微粒子分散水溶液を超音波照射装置((株)エスエムテー製、型式:UH−600S)を用いて、40分間撹拌を行った。
Next, the present invention will be described more specifically with reference to examples. The present invention is not limited to these examples.
[Example 1]
(1) Preparation of copper fine particle dispersed aqueous solution 0.2 g of copper hydroxide (Cu (OH) 2 ) was dissolved in 50 ml of ammonia water having a concentration of 0.5 mol / L, and 0.5 mol / L ammonium acetate was further added. The pH was adjusted to 10 to obtain a solution containing a copper ammine complex. Next, 0.5 g of polyvinylpyrrolidone was added to this solution and dissolved by stirring, and then the temperature between the platinum plate cathode (cathode electrode) (single side 16 mm 2 ) and the platinum plate anode (anode electrode) was 25 ° C. in the solution. Then, a reduction reaction was performed by energizing for 1 minute. At this time, the applied current density was set to 25 mA / mm 2 or less. As described above, a copper fine particle dispersed aqueous solution in which copper fine particles were dispersed in an aqueous solution was obtained.
(2) Concentration of copper fine particle-dispersed aqueous solution The copper fine particle-dispersed aqueous solution is irradiated with ultrasonic waves of 1.6 MHz and 12 W for 1 hour from below the liquid surface to the gas phase at 30 ° C. to concentrate the copper fine particles. A copper fine particle dispersed aqueous solution having a copper fine particle concentration of 10% by mass was obtained. The copper fine particle-dispersed aqueous solution was stirred for 40 minutes using an ultrasonic irradiation apparatus (manufactured by SMT Co., Ltd., model: UH-600S).
(3)焼成膜の作製
上記濃縮して得られた銅微粒子分散水溶液を撹拌終了後、15分経過してから、インクジェット用ヘッド(メクト社製:MICROJET(登録商標) Model MJ−040)に入れ、幅が700mm、厚みが100μmの透明なポリエチレンナフタレート樹脂(PEN)フィルム(帝人デュポンフィルム(株)製、品番;Q51)上に微粒子分散水溶液で格子状パターンを形成した。このときの格子状パターンは、線の幅が10μmであり、線間のピッチが100μmとなるように形成した。
形成した配線パターンを、アルゴンガス雰囲気中において、約150℃で30分間保持して塗膜を乾燥させた後、さらに窒素雰囲気中、200℃で1時間熱処理を行った。その後熱処理炉中でゆっくりと室温まで炉冷し、配線回路パターンを得た。
(4)焼結膜の導電性評価
直流四端子法(使用測定機:ケースレー社製、デジタルマルチメータDMM2000型(四端子電気抵抗測定モード))を用いて、焼結して得られた上記配線回路パターンの配線の電気抵抗を測定した。測定値は、5.6×10−5(Ω・cm)であった。
(3) Preparation of fired film After stirring the copper fine particle-dispersed aqueous solution obtained by the above concentration, 15 minutes have passed, and then put into an inkjet head (MECT Corporation: MICROJET (registered trademark) Model MJ-040). On a transparent polyethylene naphthalate resin (PEN) film having a width of 700 mm and a thickness of 100 μm (manufactured by Teijin DuPont Films Co., Ltd., product number: Q51), a lattice pattern was formed with a fine particle dispersed aqueous solution. The grid pattern at this time was formed such that the line width was 10 μm and the pitch between the lines was 100 μm.
The formed wiring pattern was held at about 150 ° C. for 30 minutes in an argon gas atmosphere to dry the coating film, and then heat-treated at 200 ° C. for 1 hour in a nitrogen atmosphere. Thereafter, the furnace was slowly cooled to room temperature in a heat treatment furnace to obtain a wiring circuit pattern.
(4) Conductivity evaluation of sintered film The above wiring circuit obtained by sintering using a DC four-terminal method (use measuring machine: digital multimeter DMM2000 type (four-terminal electric resistance measurement mode) manufactured by Keithley) The electrical resistance of the pattern wiring was measured. The measured value was 5.6 × 10 −5 (Ω · cm).
[実施例2]
実施例1で使用したと同様の水酸化銅0.2gを濃度1mol/Lのアンモニア水50mlに溶解させ、さらに1mol/Lの炭酸アンモニウムを添加してpHを11に調整し、銅アンミン錯体を含む溶液を調製した。
次に、この溶液にポリビニルピロリドン0.5gを添加して攪拌溶解させた後、溶液中で白金板陰極(カソード電極)(片面16mm2)と白金板陽極(アノード電極)と間を25℃で1分間通電し還元反応を行った。この時、印加した電流密度は25mA/mm2以下とした。以上のようにして、銅微粒子が水溶液中に分散した銅微粒子分散水溶液を得た。
この銅微粒子分散水溶液を、30℃において、1.6MHz、12Wの超音波を液面下から気相に向かって1時間照射して銅微粒子の濃縮を行い、銅微粒子濃度が10質量%の銅微粒子分散水溶液を得た。この銅微粒子分散水溶液を実施例1で行ったと同様の撹拌を行った後、実施例1と同じ方法で配線回路パターンを形成し、その配線の電気抵抗を測定した。測定値は、4.6×10−5(Ω・cm)であった。
[Example 2]
0.2 g of the same copper hydroxide used in Example 1 was dissolved in 50 ml of ammonia water having a concentration of 1 mol / L, and 1 mol / L ammonium carbonate was further added to adjust the pH to 11, so that a copper ammine complex was obtained. A containing solution was prepared.
Next, 0.5 g of polyvinyl pyrrolidone was added to this solution and dissolved by stirring, and then the platinum plate cathode (cathode electrode) (single side 16 mm 2 ) and the platinum plate anode (anode electrode) were placed at 25 ° C. in the solution. The reduction reaction was conducted by energizing for 1 minute. At this time, the applied current density was set to 25 mA / mm 2 or less. As described above, a copper fine particle dispersed aqueous solution in which copper fine particles were dispersed in an aqueous solution was obtained.
This copper fine particle dispersed aqueous solution was irradiated with ultrasonic waves of 1.6 MHz and 12 W at 30 ° C. for 1 hour from below the liquid surface to the gas phase to concentrate the copper fine particles, and the copper fine particle concentration was 10% by mass. A fine particle dispersed aqueous solution was obtained. After stirring this copper fine particle dispersed aqueous solution in the same manner as in Example 1, a wiring circuit pattern was formed by the same method as in Example 1, and the electrical resistance of the wiring was measured. The measured value was 4.6 × 10 −5 (Ω · cm).
[実施例3]
実施例1(1)に記載したのと同様の方法で調製した銅微粒子分散水溶液に、エチレングリコール濃度が20質量%となるようにエチレングリコールを添加した。この銅微粒子分散水溶液を、30℃において、1.6MHz、12Wの超音波を液面下から気相に向かって40分間照射して銅微粒子の濃縮を行い、銅微粒子濃度が10質量%の銅微粒子分散水溶液を得た。
この銅微粒子分散水溶液を実施例1で行ったと同様の撹拌を行った後、実施例1と同じ方法で配線回路パターンを形成し、その配線の電気抵抗を測定した。測定値は、2.3×10−5(Ω・cm)であった。
[Example 3]
Ethylene glycol was added to an aqueous copper fine particle dispersion prepared by the same method as described in Example 1 (1) so that the ethylene glycol concentration was 20% by mass. The copper fine particle dispersed aqueous solution is irradiated with ultrasonic waves of 1.6 MHz and 12 W at 30 ° C. from the liquid surface toward the gas phase for 40 minutes to concentrate the copper fine particles, and the copper fine particle concentration is 10% by mass. A fine particle dispersed aqueous solution was obtained.
After stirring this copper fine particle dispersed aqueous solution in the same manner as in Example 1, a wiring circuit pattern was formed by the same method as in Example 1, and the electrical resistance of the wiring was measured. The measured value was 2.3 × 10 −5 (Ω · cm).
[実施例4]
実施例1に記載したのと同様の方法で調製した銅微粒子濃度が10質量%の銅微粒子分散水溶液10mlに、エチレングリコール2.8mlを添加して、銅微粒子濃度が8質量%の銅微粒子分散水溶液12.8mlを得た。この銅微粒子分散水溶液を実施例1で行ったと同様の撹拌を行った後、実施例1と同じ方法で配線回路パターンを形成し、その配線の電気抵抗を測定した。測定値は、1.1×10−5(Ω・cm)であった。
[Example 4]
2.8 ml of ethylene glycol was added to 10 ml of a copper fine particle dispersion aqueous solution having a copper fine particle concentration of 10% by mass prepared by the same method as described in Example 1, and a copper fine particle dispersion having a copper fine particle concentration of 8% by mass was then added. 12.8 ml of aqueous solution was obtained. After stirring this copper fine particle dispersed aqueous solution in the same manner as in Example 1, a wiring circuit pattern was formed by the same method as in Example 1, and the electrical resistance of the wiring was measured. The measured value was 1.1 × 10 −5 (Ω · cm).
[実施例5]
実施例1(1)に記載したのと同様の方法で調製した銅微粒子分散水溶液を、遠心分離処理機を使用して銅微粒子を回収した。回収した該銅微粒子を、濃度0.5mol/Lのアンモニア水50mlに0.5mol/Lの酢酸アンモニウムを添加してpHを10に調整したアルカリ水溶液中に分散させた。
その後は、実施例1(2)〜(4)に記載したと同様にして作製した配線回路パターンの配線の電気抵抗を測定した。電気抵抗の測定値は、5.9×10−5(Ω・cm)であった。
[Example 5]
Copper fine particles were recovered from a copper fine particle-dispersed aqueous solution prepared by the same method as described in Example 1 (1) using a centrifugal separator. The recovered copper fine particles were dispersed in an aqueous alkali solution adjusted to pH 10 by adding 0.5 mol / L ammonium acetate to 50 ml of ammonia water having a concentration of 0.5 mol / L.
Thereafter, the electrical resistance of the wiring of the wiring circuit pattern produced in the same manner as described in Example 1 (2) to (4) was measured. The measured value of electrical resistance was 5.9 × 10 −5 (Ω · cm).
[比較例1]
比較用の銅微粒子分散水溶液として、(株)アルバック製、銅ナノ粒子分散液(商品名:Cuナノメタルインク「Cu1T」)を用いた。この銅ナノ粒子分散液を、実施例1と同様の条件でPENフィルム上に格子状パターンを形成したが、パターン形成後、インクが基板を溶解することにより線が滲んで線の幅が10μmから50μmまで広がり、所望の微細な配線回路パターンを得ることができなかった。
[Comparative Example 1]
As a copper fine particle dispersion aqueous solution for comparison, a copper nanoparticle dispersion (trade name: Cu nanometal ink “Cu1T”) manufactured by ULVAC, Inc. was used. With this copper nanoparticle dispersion, a lattice-like pattern was formed on the PEN film under the same conditions as in Example 1. However, after the pattern was formed, the ink was dissolved in the substrate, so that the line was blurred and the line width was 10 μm. It spreads to 50 μm, and a desired fine wiring circuit pattern could not be obtained.
[比較例2]
1mol/Lの炭酸アンモニウムの代わりに1mol/Lのイオウ化合物である硫酸アンモニウムを添加してpHを11に調整した以外は実施例2に記載したのと同じ方法で銅微粒子分散水溶液を調製し、配線回路パターンを形成した。
得られた配線回路パターンについて、実施例1と同様に配線の電気抵抗を測定したところ、導電性を示さなかった。
上記のように、実施例1、2で形成した配線回路は、200℃での熱処理により良好な電気伝導性を示すことが確認された。一方、還元反応の系にイオウ化合物を含む比較例2で形成した配線回路は、導電性を示さなかった。
[Comparative Example 2]
A copper fine particle-dispersed aqueous solution was prepared by the same method as described in Example 2 except that ammonium sulfate, which is a 1 mol / L sulfur compound, was added instead of 1 mol / L ammonium carbonate to adjust the pH to 11, and wiring was prepared. A circuit pattern was formed.
For the obtained wiring circuit pattern, the electrical resistance of the wiring was measured in the same manner as in Example 1. As a result, it did not show conductivity.
As described above, it was confirmed that the wiring circuits formed in Examples 1 and 2 showed good electrical conductivity by heat treatment at 200 ° C. On the other hand, the wiring circuit formed in Comparative Example 2 containing a sulfur compound in the reduction reaction system did not exhibit conductivity.
[実施例6]
実施例1に記載したのと同様の方法で銅微粒子分散水溶液を調製し、調製した銅微粒子分散水溶液を、ゴム栓付きのブローバッグ内に移し、乾燥窒素ガスを充填して気密封止した。この状態で銅微粒子分散水溶液を30日間保管した後、実施例1に記載したのと同様の方法で配線回路パターンを形成した。配線回路パターン形成の際には、シリコンゴム管のついた注射針をブローバッグのゴム栓に刺してインクを吸出し、インクジェットカートリッジへの充填を行うことで、銅微粒子分散水溶液を大気に晒さずにインクジェットカートリッジに移送した。このようにして得られた配線回路パターンについて、実施例1と同様に配線の電気抵抗を測定した。測定値は、2.3×10−5(Ω・cm)であった。
[Example 6]
A copper fine particle-dispersed aqueous solution was prepared in the same manner as described in Example 1, and the prepared copper fine particle-dispersed aqueous solution was transferred into a blow bag equipped with a rubber stopper, filled with dry nitrogen gas, and hermetically sealed. After storing the copper fine particle dispersed aqueous solution in this state for 30 days, a wiring circuit pattern was formed in the same manner as described in Example 1. When forming a wiring circuit pattern, the injection needle with a silicone rubber tube is inserted into the rubber stopper of the blow bag to suck out the ink and fill the ink jet cartridge without exposing the aqueous copper fine particle dispersion to the atmosphere. It was transferred to an inkjet cartridge. For the wiring circuit pattern thus obtained, the electrical resistance of the wiring was measured in the same manner as in Example 1. The measured value was 2.3 × 10 −5 (Ω · cm).
[比較例3]
実施例1に記載したのと同様の方法で銅微粒子分散水溶液を調製し、調製した銅微粒子分散水溶液をガラスビンに入れ、大気中で1時間静置した後、実施例1に記載したのと同様の方法で配線回路パターンを形成した。得られた配線回路パターンについて、実施例1と同様に配線の電気抵抗を測定した。測定値は、2.2×10−3(Ω・cm)であった。
[Comparative Example 3]
A copper fine particle-dispersed aqueous solution was prepared in the same manner as described in Example 1, and the prepared copper fine particle-dispersed aqueous solution was placed in a glass bottle and allowed to stand in the atmosphere for 1 hour, and then the same as described in Example 1 A wiring circuit pattern was formed by the method described above. For the obtained wiring circuit pattern, the electrical resistance of the wiring was measured in the same manner as in Example 1. The measured value was 2.2 × 10 −3 (Ω · cm).
[比較例4]
実施例1に記載したのと同様の方法で銅微粒子分散水溶液を調製し、調製した銅微粒子分散水溶液をガラスビンに入れ、大気中で30日間保管した。30日後に銅微粒子分散水溶液を観察すると、ガラスビンの底に沈殿物が生じていた。この銅微粒子分散水溶液をインクジェットカートリッジに充填し、配線回路パターン形成を試みたが、インクジェットヘッド内でインク詰まりが発生し、配線回路パターンは形成できなかった。
実施例6のように、銅微粒子分散水溶液が入った保管容器へ、乾燥状態の不活性ガスを充填して気密封止して保管した銅微粒子分散水溶液から形成した配線回路は、200℃での熱処理により良好な電気伝導性を示すことが確認された。一方、比較例3のように銅微粒子分散水溶液を大気に晒して保管した場合は、銅微粒子分散水溶液から形成した配線回路の導電性が低く、さらに、比較例4のように、銅微粒子分散水溶液を長期間大気中に晒して保管した場合は、銅微粒子分散水溶液が変質し、保存安定性が悪かった。
[Comparative Example 4]
A copper fine particle-dispersed aqueous solution was prepared in the same manner as described in Example 1, and the prepared copper fine particle-dispersed aqueous solution was placed in a glass bottle and stored in the atmosphere for 30 days. When the copper fine particle-dispersed aqueous solution was observed 30 days later, a precipitate was formed at the bottom of the glass bottle. The copper fine particle-dispersed aqueous solution was filled into an ink jet cartridge and an attempt was made to form a wiring circuit pattern. However, ink clogging occurred in the ink jet head, and the wiring circuit pattern could not be formed.
As in Example 6, the wiring circuit formed from the copper fine particle dispersed aqueous solution that was stored in a storage container containing the copper fine particle dispersed aqueous solution by being filled with an inert gas in a dry state and hermetically sealed was stored at 200 ° C. It was confirmed that the heat treatment showed good electrical conductivity. On the other hand, when the copper fine particle dispersed aqueous solution is stored exposed to the air as in Comparative Example 3, the conductivity of the wiring circuit formed from the copper fine particle dispersed aqueous solution is low. Further, as in Comparative Example 4, the copper fine particle dispersed aqueous solution is used. Was stored in the atmosphere for a long period of time, the aqueous copper fine particle dispersion was altered and the storage stability was poor.
Claims (12)
(i)銅イオンを、分散剤の存在下でpH調整剤によりpH9.2以上に調整したアンモニア水溶液中でアンモニアと下記反応をさせ、水溶性の銅アンミン錯体を得る工程(工程1)、
Cu2++4NH3 → [Cu(NH3)4]2+
又は Cu2++4NH4(OH) → [Cu(NH3)4]2+ +4H2O
(ii)前記工程1で得られた銅アンミン錯体を含む還元反応水溶液において、下記の銅アンミン錯体の電解還元反応により、少なくとも表面の一部が分散剤で覆われた銅微粒子を形成する工程(工程2)、
Cu(NH3)4 2++2e− → Cu+2NH3
又は Cu(NH3)4 2++2e−+2H2O→ Cu+2NH4(OH)
を含み、前記還元反応の系において、銅元素、炭素原子、水素原子、酸素原子、及び窒素原子以外の原子を含む化合物を含まずに製造された銅微粒子分散水溶液を
基材上に配置して、乾燥後に焼成して形成されたことを特徴とする導電部材。 A copper fine particle-dispersed aqueous solution in which copper fine particles having an average particle size of 1 to 150 nm of primary particles are dispersed in an aqueous solution in which at least part of the surface is covered with a dispersant,
(I) a step of obtaining a water-soluble copper ammine complex by reacting copper ions with ammonia in an aqueous ammonia solution adjusted to a pH of 9.2 or more with a pH adjuster in the presence of a dispersant (step 1);
Cu 2+ + 4NH 3 → [Cu (NH 3 ) 4 ] 2+
Or Cu 2+ + 4NH 4 (OH) → [Cu (NH 3 ) 4 ] 2+ + 4H 2 O
(Ii) In the reduction reaction aqueous solution containing the copper ammine complex obtained in the step 1, the step of forming copper fine particles in which at least a part of the surface is covered with the dispersant by the electrolytic reduction reaction of the following copper ammine complex ( Step 2),
Cu (NH 3 ) 4 2+ + 2e − → Cu + 2NH 3
Or Cu (NH 3 ) 4 2+ + 2e − + 2H 2 O → Cu + 2NH 4 (OH)
In the reduction reaction system, a copper fine particle dispersed aqueous solution produced without containing a compound containing an element other than a copper element, a carbon atom, a hydrogen atom, an oxygen atom, and a nitrogen atom is disposed on a substrate. A conductive member formed by firing after drying.
前記分子中に2以上の水酸基を有する多価アルコールが、エチレングリコ−ル、ジエチレングリコ−ル、1,2−プロパンジオ−ル、1,3−プロパンジオ−ル、1,2−ブタンジオ−ル、1,3−ブタンジオ−ル、1,4−ブタンジオ−ル、2−ブテン−1,4−ジオール、2,3−ブタンジオ−ル、ペンタンジオ−ル、ヘキサンジオ−ル、オクタンジオ−ル、グリセロール、1,1,1−トリスヒドロキシメチルエタン、2−エチル−2−ヒドロキシメチル−1,3−プロパンジオール、1,2,6−ヘキサントリオール、1,2
,3−ヘキサントリオール、1,2,4−ブタントリオール、グリセロ−ル、トレイトレイトール、エリトリト−ル、ペンタエリスリト−ル、ペンチト−ル、キシリトール、リビトール、アラビトール、ヘキシト−ル、マンニトール、ソルビトール、ズルシトール、グリセリンアルデ、ジオキシアセトン、トレオース、エリトルロース、エリトロース、アラビノース、リボース、リブロース、キシロース、キシルロース、リキソース、グルコ−ス、フルクト−ス、マンノース、イドース、ソルボース、グロース、タロース、タガトース、ガラクトース、アロース、アルトロース、ラクト−ス、キシロ−ス、アラビノ−ス、イソマルト−ス、グルコヘプト−ス、ヘプト−ス、マルトトリオース、ラクツロース、及びトレハロースの中から選択される1種又は2種以上であり、
並びに、前記アルカノールアミンが、ジメタノールアミン、トリメタノールアミン、ジエタノールアミン、トリエタノールアミン、ジイソプロパノールアミン、トリイソプロパノールアミン、N−メチルジエタノールアミン、N−エチルジエタノールアミン、及びN−n−ブチルジエタノールアミンの中から選択される1種又は2種以上である、請求項9に記載の導電部材。 The alcohol having 3 to 8 carbon atoms is one or more selected from 1-propanol, 2-propanol, 2-butanol, 2-methyl 2-propanol,
The polyhydric alcohol having two or more hydroxyl groups in the molecule is ethylene glycol, diethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2-butene-1,4-diol, 2,3-butanediol, pentanediol, hexanediol, octanediol, glycerol, 1, 1,1-trishydroxymethylethane, 2-ethyl-2-hydroxymethyl-1,3-propanediol, 1,2,6-hexanetriol, 1,2
, 3-hexanetriol, 1,2,4-butanetriol, glycerol, trayolitol, erythritol, pentaerythritol, pentitol, xylitol, ribitol, arabitol, hexitol, mannitol, sorbitol , Dulcitol, glycerin alde, dioxyacetone, threose, erythrulose, erythrose, arabinose, ribose, ribulose, xylose, xylulose, lyxose, glucose, fructose, mannose, idose, sorbose, growth, talose, tagatose, galactose, Selected from allose, altrose, lactose, xylose, arabinose, isomaltose, glucoheptose, heptose, maltotriose, lactulose, and trehalose It is one or two or more that,
And the alkanolamine is selected from dimethanolamine, trimethanolamine, diethanolamine, triethanolamine, diisopropanolamine, triisopropanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, and Nn-butyldiethanolamine. The electrically-conductive member of Claim 9 which is 1 type, or 2 or more types.
The copper fine particle-dispersed aqueous solution disposed on the substrate is subjected to ultrasonic irradiation, filtration with a reverse osmosis membrane, filtration with an ultrafiltration membrane, vacuum dehydration, or the copper fine particle-dispersed aqueous solution obtained in claim 9 or 10. By freeze-drying, one or more kinds selected from water present in the aqueous copper fine particle dispersion, alcohol having 3 to 8 carbon atoms, polyhydric alcohol having two or more hydroxyl groups in the molecule, and alkanolamine The conductive member according to claim 9 or 10, wherein the conductive member is a dispersed aqueous solution having a copper fine particle concentration in an aqueous solution of 1 to 60% by mass obtained by removing a part thereof.
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